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In this work, plane tree seed-based activated carbons were characterized in detail for a variety of applications. The particularly important area of application would be in the artificial photosynthesis. After carbonization process of biomass precursor at 650°C, the resulting preliminary activated carbons were activated at various temperatures. The activated carbons were characterized by oxygen functionalities (a particularly important role has ester oxygen groups) which provide a unique microstructure. The chemical compositions of as-prepared activated carbons were analyzed through Fourier transform infrared and Raman spectra as well as gas chromatography–mass spectroscopy analysis, while morphology was observed by scanning electron microscopy analysis. Applied analysis showed that detected graphite mainly becomes uniformly nanocrystalline system. The current study also explored the applicability of carbon material obtained from plane tree seed as a potential gaseous adsorbent. The characterization showed that the tested material contains both mesopores and micropores, and this should be advantageous for the gas sorption process, since mesopores may provide low-resistant pathways for the diffusion of CO2 molecules, while the micropores are the most suitable for trapping of CO2. The sorption process analysis (including adsorption/desorption isotherms behavior) shows indication that the rate-limiting step of CO2 adsorption onto activated carbon is probably governed by diffusion-controlled process, especially at temperatures below 850°C.

Abstract Slow pyrolysis characterization and kinetic modeling study of five different biomasses (corn brakes (CB), wheat straw (WS), hazelnut shell (HS), sawdust (Beech), and sawdust chemically treated (SDCT)) were performed in this work, using STA-MS techniques. Thermal decomposition of these samples was divided into three stages corresponding to removal of water, devolatilization, and formation of bio-char. Mass spectrometry (MS) showed that H2, CH4, H2O, CO2 (C3H8), CO, and C2H6 were the main gaseous products released during the pyrolysis of biomasses. It was found that H2O, CO and CO2 evolutions for all biomass samples arise from lignin source in biomass, followed by the cellulose, and hemicelluloses. It was established that the pseudo-component fraction estimated by the theoretical calculations is dependent on the heating rate. Using Gaussian multi-peak fitting and peak-to-peak approaches, regardless of the type of biomass, it was found that decomposition of lignin occurs independently of decomposition of remaining two pseudo-components and that there is no interaction between them. Namely, it was assumed that during pyrolysis process of biomasses, carbohydrate (hemicelluloses + cellulose)—lignin chemical structures most likely exist, where the variety of lignin structure units in different types of biomass affects on the level of energy required for its decomposition.

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.

As waste biomass from fruit processing industry, apricot kernel shells have a potential for conversion to renewable energy through a thermo-chemical process such as pyrolysis. However, due to major differences of biomass characteristics as the well-known issue, it is extremely important to perform detailed analysis of biomass samples from the same type (or same species) but from different geographical regions. Regarding full characterization of considered biomass material and to facilitate further process development, in this paper, the advanced mathematical model for kinetic analysis was used. All performed kinetic modeling represents the process kinetics developed and validated on thermal decomposition studies using simultaneous thermogravimetric analysis (TGA) - differential thermal analysis (DTA) - mass spectrometry (MS) scanning, at four heating rates of 5, 10, 15 and 20 degrees C min(-1), over temperature range 30-900 degrees C and under an argon (Ar) atmosphere. Model-free analysis for base prediction of decomposition process and deconvolution approach by Fraser-Suzuki functions were utilized for determination of effective activation energies (E), pre-exponential factors (A) and fractional contributions (u), as well as for separation of overlapping reactions. Comparative study of kinetic results with emission analysis of evolved gas species was also implemented in order to determine the more comprehensive pyrolysis kinetics model. Obtained results strongly indicated that the Fraser-Suzuki deconvolution provides excellent quality of fits with experimental ones, and could be employed to predict devolatilization rates with a high probability. From energy compensation effect properties, it was revealed the existence of unconventional thermal lag due to heat demand by chemical reaction.

Thermo-analytical characterization of selected biomasses (agricultural waste and wood biomass feedstock) through the pyrolysis process was performed under dynamic conditions. Slow pyrolysis (carbonization) regime (with a heating rate below 50 degrees C min(-1)) was selected because it favours the residual solid (bio-carbon/bio-char) in the higher yields (change in the surface area of bio-char with pyrolysis conditions was dependent on the type of biomass feedstock). Comparison of results and discussions related to obtained percentage pyro char yields from thermo-chemical conversion of biomass feedstocks were generated from simultaneous thermal analysis (STA) (TGA-DTG-DTA apparatus). The analysis of gaseous products of pyrolysis was carried out using mass spectrometry (MS) technique. Releasing of the light gaseous compounds (mainly CO, CO2, CH4, and H-2 non-condensable gases) was monitored simultaneously with TGA measurements. Discussion related to this issue was performed from the aspect of the syngas production, as well as the versatility of selected biomasses in the gasification process where the various gasifying agent may be in use.

Rhyolite is an extrusive, igneous rock of aluminosilicate composition that upon rapid cooling forms obsidian. Obsidian is amorphous and contains limited water portions ( 5 mass%). In the current study, kinetics of hydrous rhyolite dehydration were investigated by thermogravimetry up to 1000 °C, at heating rates of 2.5, 5, 10 and 20 °C min−1 and under inert atmosphere. The mass loss is approx. 7.6 mass%, occurs along wide temperature range (100–800 °C) and is solely attributed to the release of molecular water ((H2O)m) and hydroxyl groups (OH). Rhyolite dehydration was considered as a solid-state reaction, and the apparent activation energy (Ea) of dehydration was calculated throughout the whole conversion range (a) by applying the isoconversional Friedman and advanced Vyazovkin methods. Both methods revealed inverse sigmoid trend in Ea values versus conversion degree, possessing almost stable value of 61 ± 5 kJ mol−1 for Friedman method and 59.44 kJ mol−1 for Vyazovkin method on conversion range between 0.25 and 0.75, and sharp increase at higher conversion degree. The intensive change in Ea during dehydration progression is attributed to the change in releasing species (from (H2O)m to OH). Raman and FT-IR spectroscopy analyses of raw and partially dehydrated samples at different stages revealed that up to 300 °C mainly (H2O)m is diffused out of the material causing sample enrichment in OH groups. OH release, which occurs at relatively higher temperature, is accompanied by increase in apparent Ea value of dehydration. Concerning microstructure of raw rhyolite, it exhibits a network of micro-fractures which serve as water release routes. Upon heating, more and wider fractures are created. At 600 °C, fractures merging occurs creating voids, which constitute forerunners of the expansion phenomenon. Further temperature increase causes material softening allowing local plastic deformation, which under the high pressure that is exerted by the releasing water species incites the formation of large cavities and fractures, initiating expansion.

This study presents the experimental results of the mechanical and thermophysical properties of wood pellet samples important for their utilization in pellet stoves and boilers for heat production. The impact of operational parameters during the production process on a single pelletizer unit for three typical domestic commercial wood pellet samples (PWP110, BWP110, and BWP140) on fuel particle mechanical characteristics and related thermal properties was analyzed. It was concluded that the changes in raw material selection, as well as related operating parameters (extrusion length, i.e., die temperature during production process), have influenced the key mechanical and thermal characteristics of tested commercial wood pellets. The presented results have indicated the existence of a thin solid layer (due to waxes and subsequently lignin coating layer behaviors depending on their glass transition temperatures) on the surface of the BWP140 pellet sample. This layer leads to increasing the thermal resistance in the considered sample which can be explained by decreasing the effective thermal conductivity. Also, the forming of this layer on the surface of the wood pellet sample was caused by the production process (high-temperature impact explained by increasing friction between the die and feedstock during pellets production). It could be related to a lower value of effective thermal conductivity and specific heat capacity for considered (Beech) wood pellet sample.

As representative among biomass feedstocks, Poplar fluff was chosen to analyze the pyrolysis properties of this new biofuel. Thermogravimetry under inert (argon) atmosphere at the heating rates of 5, 10, 15, and 20 °C min−1 was employed in the investigation of thermal processing of studied biomass. The determination of kinetic parameters and estimation of reaction mechanism function were done through application of the state-of-the-art NETZSCH Kinetics NEO software. With this aim, the various model-free models and model-based calculations were implemented. The obtained results showed that the most appropriate kinetic model to describe the thermal decomposition of Poplar fluff sample was n-dimensional acceleratory Avrami–Erofeev model (An) for three-step consecutive reaction mechanism. Governed reaction pathway in pyrolysis process represents fragmentation reactions which arise from levoglucosan decomposing that permits permanent gases and refractory tars, where diffusion-controlled process is involved in the sample devolatilization. The modulated and multiple-step predictions of pyrolysis process were also carried out.