Search Results (116)

This study aimed to investigate the effect of wildfire episodes on air quality in terms of particulate matter (PM) and carbonaceous compound concentration in ambient air, and to assess deviations from typical annual patterns. The sampling was performed at a rural background site near the Adriatic coast in Croatia through 2024. To better understand contributions caused by fire events, the levels of organic carbon (OC), elemental carbon (EC), black carbon (BC), pyrolytic carbon (PyrC), optical carbon (OptC), water-soluble organic carbon (WSOC), levoglucosan (LG), mannosan (MNS), and galactosan (GA) were determined in PM₁₀ and PM_2.5 fractions (particles smaller than 10 µm and 2.5 µm, respectively). The annual mean concentrations of PM₁₀ and PM_2.5 were 14 µg/m³ and 8 µg/m³, respectively. During the fire episode, the PM_2.5 mass contribution to the total PM₁₀ mass exceeded 65%. Total carbon (TC) and OC increased by a factor of 7, EC and BC by 12, PyrC by 8, and WSOC by 12. The concentration of LG reached 1.219 μg/m³ in the PM₁₀ fractions and 0.954 μg/m³ in the PM_2.5 fractions, representing a 200-fold increase during the fire episode. Meteorological data were integrated to assess atmospheric conditions during the fire episode, and the specific ratios between fire-related compounds were analyzed. Full article

The present study investigates the catalytic conversion of low-density polyethylene (LDPE) into high-grade fuel oil using a semi-batch reactor at 350 °C under ambient pressure, with a catalyst-to-LDPE ratio of 1:20. Zeolite-based catalysts were synthesized by impregnating different metals (Fe, Zn, Cr, Mn, and Ga) onto ZSM-5 with a silica-to-alumina ratio of 30 (Z30). These catalysts were characterized using BET, XRD, and NH3-TPD techniques to evaluate their physicochemical properties. The results showed that catalytic pyrolysis of LDPE yielded less pyrolytic oil compared to non-catalytic pyrolysis. The obtained pyrolytic oil was analysed through elemental composition, gross calorific value (GCV), Simulated Distillation, and GC-DHA. The elemental analysis revealed a high carbon (85–86%) and hydrogen (13–14%) content, resulting in a high GCV of approximately 42 MJ/kg. GC-DHA analysis indicated that the pyrolytic oil was rich in aromatic and olefinic compounds. Among the catalysts, 5Fe/Z30 exhibited the highest aromatic selectivity (35%), a research octane number of 91, and 100% LDPE conversion. These findings underscore the potential of low-cost iron-based catalysts for efficiently converting LDPE waste into valuable chemicals and fuels. Full article

This paper presents the results of naturally aspirated compression ignition (CI) internal combustion engine (ICE) bench tests of fuels in the form of a blend of diesel oil with recycled oil (RF) in the form of tire pyrolysis oil (TPO) as an admixture with the content of pyrolytic oil with the blend being 10% m/m (D90+RF10). The results relate to reference conditions in which the engine is fed with pure diesel oil (D100). The experiment included the evaluation of engine performance and the determination of the content of selected substances in the exhaust gas for brake-set engine loads equal to 5 Nm, 10 Nm, 15 Nm, and 20 Nm. For each load, engine operating parameters and emissions of selected exhaust components were recorded at preset speeds in the range of 1400–2400 rpm for each engine load. The hourly fuel consumption and exhaust gas temperature were determined. The contents of CO₂, CO, and HC in the exhaust gas were measured. The consumption of D90+RF10 increased by 56%, and CO₂ emissions were 21.7% higher at low loads. The addition of sulfur-containing pyrolytic oil as an admixture to diesel oil resulted in SO_x emissions. The results show the suitability of pyrolytic oil and the possibility of using it as an admixture to fossil fuels. In order to meet SO_x emission levels in land-based installations and for vehicle propulsion, it is necessary to desulfurize fuel or desulfurize deSO_x exhaust gas systems. The CO and HC emission levels in the exhaust gases from the engine powered by the D90+RF10 fuel meet current requirements for motor vehicle exhaust composition. Full article

5-aminotetrazole (5AT)-based gas generators, particularly the 5AT/NaIO₄ system, have garnered interest for their high gas production and energy potential. This study investigates the impact of various metal oxides (MnO₂, Al₂O₃, TiO₂, CuO, Fe₂O₃, MgO, ZnO, and MoO₃) on the thermal decomposition and combustion performance of 5AT/NaIO₄. The REAL calculation program was used to infer reaction products, which indicated that the gas products are almost all harmless, with negligibly low percentages of NO and CO. Thermogravimetric analysis revealed that metal oxides, especially MoO₃, significantly advance the decomposition process above 400 °C, reducing the activation energy by 130 kJ/mol and lowering critical ignition and thermal explosion temperatures. Combustion performance tests and closed bomb tests confirmed MoO₃’s positive effect, accelerating reaction rates and enhancing decomposition efficiency. The system’s high Gibbs free energy indicates non-spontaneous reactions. These findings provide valuable insights for designing environmentally friendly gas generators, highlighting MoO₃’s potential as an effective catalyst. Full article

The use of tomato plant residues (i.e., stems, leaves, etc.) as a substrate for catalytic pyrolysis of biomass was investigated. A comprehensive study was conducted to investigate the impact of catalysts on the performance of different pyrolysis fractions (i.e., gas, biosolid, waxes, and bioliquid) as well as the distribution of products within the bioliquid. The catalysts employed in this study were derived from two distinct types of zirconia. The first type was synthesized by a conventional sol-gel method, while the second type was prepared with a modified method aimed at improving the presence of mesopores. This modification involved the incorporation of Pluronic 123. These materials were designated ZrO₂ and ZrO₂P25, respectively. Both types of zirconia were used as supports for tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), a heteropolyacid with a Keggin structure, in the preparation of catalysts with strong acid sites. The results demonstrated that the bioliquid yield of the non-catalytic fast pyrolysis of tomato plant waste was approximately 23% and that the obtained bioliquid contained a wide variety of molecules, which were detected and quantified by GC-MS. In the presence of the catalysts, both the bioliquid yield and the distribution of bioliquid products were substantially modified. Furthermore, the possible sugar degradation pathways leading to the formation of the molecules present in the pyrolytic bioliquids were thoroughly examined. The results obtained from this study indicate that the physicochemical characteristics of the catalysts, specifically their pore size and acidity, have a significant impact on the selectivity of the catalytic processes towards valuable molecules, including anhydro-sugars and furanic derivatives such as furfural and furfuryl alcohol. Full article

Sustainable hydrocarbons are one of the main methods of decreasing the use of fossil fuels and derivatives, contributing to the mitigation of environmental impacts and greenhouse gas emissions. Circular economic concepts focus on reusing waste by converting it into new products, which are then input again into industrial production lines, thus decreasing the necessity of fossils. Polypropylene-based plastic waste can be depolymerized into smaller chemical chains, producing a liquid phase rich in hydrocarbons. In the same way, triacylglycerol-based waste biomasses can also be converted into renewable hydrocarbons. Our research studied the co-processing of polypropylene (PP) and cottonseed oil dreg (BASOs) waste from the biodiesel industry using a micropyrolysis system at 550 °C, previously validated to predict the scale-up of the process. PP showed the production of alkanes and alkenes, while BASOs also produced carboxylic acids in addition to the PP products. The main impacts were observed in the conversion yields, reaching the highest values of pyrolytic liquid (64%), gas (14%), and solid product (13%) compared to the co-processing mixture of BASO:PP (1:2). Also, in this mixture, the production of carboxylic acids decreased to the lowest value (~10%), improving the conversion to sustainable hydrocarbons. Full article

Biomass serves as a promising renewable and sustainable feedstock for energy production through thermochemical conversion. It can be transformed into sustainable biofuels by means of pyrolysis. Among these methods, the pyrolytic poly-generation of biomass, a novel biomass thermal conversion technology, can concurrently produce three valuable products, namely biochar, bio-oil, and combustible gas, without generating any byproducts. In contrast, conventional thermal conversion processes, such as carbonization for biochar, liquefaction for bio-oil, gasification for syngas, and combustion for heat, only yield single products, have limited efficiency, and give rise to byproducts. Clearly, pyrolytic poly-generation holds significant advantages over conventional thermal conversion processes. Nevertheless, the pyrolytic poly-generation process and its products are remarkably influenced by numerous factors, including the raw biomass properties, pretreatment methods, operating parameters, and catalysts. This article reviews the processing parameters and technology for biomass pyrolytic poly-generation, and also explores future research areas, with the aim of identifying research gaps and promoting its industrial implementation. Full article

The possibility of using pyrolysis for the valorisation of leather and textile wastes constituting post-consumer clothes is analysed in this paper. The effect of gas type was investigated on the physico-chemical properties, composition, structure, and formation of the specific surfaces of carbonised materials produced by the pyrolysis process. The differences in the elemental composition of the carbonised materials derived from textile and leather wastes may be due to the specific chemical compositions. Both textile and leather wastes are rich in organic compounds, but their structural and compositional differences significantly influence the element content of carbonised materials. The characteristic feature of carbonised material made from leather waste is a relatively high nitrogen content (approx. 9 wt. %). In turn, in the case of carbonised material made from textile waste, a high carbon content is characteristic (75–80 wt. %). Moreover, G- and D-bands were detected in all the analysed carbonised materials. The presence of these bands confirms the transformation of leather and textile wastes into carbon materials. It was found that maintaining a high degree of order in the structure (calculated as I_D/I_G ratios based on the D and G peak intensities) of carbonised materials is advantageous to conducting the pyrolysis process on textile materials in N₂ and on leather materials in CO₂. The carbonised materials produced using these gases are characterised by an I_D/I_G ratio at a level of 0.05. Pyrolysis carried out in these gases also has a positive effect on the size of the BET surface area. However, it was shown that the carbonised products from textile materials are characterised by a higher BET surface area than that of carbonised products from leather materials regardless of the type of gas used during the pyrolysis process. Furthermore, all the carbonised materials are characterised by a high percentage content of mesopores in the carbon structure. These types of carbon materials have widespread application potential. The presented studies contribute data about the pyrolytic processing of post-consumer clothes (such as leather and textile waste) into carbonised materials to reuse, according to the circular economy model. Full article

This paper reports the results of a study on the significance of the inertization system configuration of a laboratory-scale fixed bed batch reactor with regard to the yield of pyrolysis oil and reactor conversion. Two typical reactor inertization systems were investigated depending on whether the carrier gas (nitrogen in this study) was added from the top or from the bottom of the reactor. Polypropylene (PP) packaging waste (100 g) was used as a model sample. A factorial experimental design was adopted for one categorical parameter, the arrangement of parts of the reactor inertization system. All experiments were conducted at 475 °C, with a carrier gas flow rate of 0.1 L/min and a reaction time of 90 min. Statistical analysis and processing of the results showed that the configuration of the inertization system had a remarkable impact on the pyrolysis oil and gas yield, while its impact on the overall reactor conversion was negligible. When applying the two observed methods of reactor inertization, the average yields of pyrolysis oil and gas differed by 1.7% and 1.8%, respectively. All of the applied statistical treatments had a significance level of 0.05, i.e., there was only a 5% chance of incorrectly rejecting the hypothesis of equality of arithmetic means of pyrolysis yields when the two different methods of reactor inertization were applied. The explanation of this behavior is attributed to the temperature change inside the reactor, which shows that this particular fixed bed reactor suffers from local overheating in its middle part. Local overheating of the middle part of the reactor is more pronounced in the case of inerting the reactor from the bottom, which leads to greater excessive cracking of volatile products compared to the mode of inerting the reactor from the top part and thus greater formation of non-condensable gases, i.e., a reduction in the yield of pyrolytic oil. Full article

This study investigates the composition, abundance, and vertical export of polycyclic aromatic hydrocarbons (PAHs) across three deep basins of the northeastern Mediterranean Sea (NEMS) over one year. Sinking particles were collected using sediment traps, and PAH analysis was conducted via gas chromatography-mass spectrometry. PAH fluxes varied significantly, peaking in the north Aegean Sea due to mesotrophic conditions, nutrient-rich riverine and Black Sea water inflows, and maritime anthropogenic inputs. The fluxes were highest in winter and lowest in fall. In the Cretan Sea, petrogenic sources (~70%) dominated, driven by currents, with fluxes highest in spring and lowest in winter. The Ionian Sea exhibited lower fluxes, peaking in summer and decreasing in fall. Atmospheric deposition seems to be the main transport pathway of pyrolytic PAHs in this site, while its high-water column depth (4300 m) compared to the other sites presumably enables extended degradation of organic constituents during particle settling. The positive matrix factorization (PMF) and principal component analysis (PCA) results reveal complementary insights into PAH sources and transport mechanisms. PMF analysis identified combustion (61%) and petrogenic (22%) sources, while PCA highlighted biogenic fluxes (57.7%) and atmospheric deposition. Seasonal productivity, riverine inputs, and water circulation shaped PAH variability, linking combustion-related PAHs to atmospheric soot and petrogenic PAHs to organic-rich particles. Full article

The paper manufacturing process produces liquid and gaseous alternative fuels, as well as solid wastes. These can be subsequently treated through chemical processing, oxidation, and thermal activation, resulting in adsorbent materials with CO₂ adsorption capacities. The valorisation of black liquor waste resulting from paper manufacturing was achieved through a catalytic pyrolysis process using two catalysts previously prepared in house (Cu-Zn-MCM-41 and Ni-SBA-16). The HCl-treated adsorbent material, resulting from Ni-SBA-16-catalysed pyrolysis, was selected for use in CO₂ adsorption tests as it had the highest specific surface area (224.06 m²/g) and pore volume (0.28 cm³/g). The adsorption experimental setup was linked to a gas chromatograph in order to evaluate CO₂ adsorption efficiency using a binary gas mixture consisting of 81% CO₂ and 19% N₂. With a CO₂ adsorption capacity of 1.61 mmol/g, a separation efficiency of 99.78%, and a CO₂ recovery yield of 90.02%, it can be concluded that the developed adsorbent material resulting from Ni-SBA16-catalysed pyrolysis and HCl treatment represents a viable solution for black liquor pyrolytic solid waste removal and reduction in greenhouse gases. Full article

The production of waste textiles has increased rapidly in the past two decades along with the rapid development of the economy, the majority of which has been either landfilled or incinerated, resulting in energy loss and environmental pollution. Microwave pyrolysis, which can transform heterogeneous and complex waste feedstocks into value-added products, is considered one of the most competitive technologies for processing waste textiles. However, achieving selective product formation during the microwave pyrolysis of waste textiles remains a significant challenge. Herein, sodium acetate, potassium acetate, and nickel acetate were introduced into waste textiles through an impregnation method as raw materials to improve the pyrolysis efficiency. The optimized process parameters indicated that nickel acetate had the most favorable promotional effect of the three acetates. Notably, the waste textiles containing 1.0% Ni exhibited the highest gas production rate, with the hydrogen-containing combustible gas reaching 81.1% and 61.0%, respectively. Using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy to characterize the waste textiles before and after pyrolysis, it was found that nickel acetate was converted into metallic nickel (Ni⁰) during microwave pyrolysis. This active site significantly enhanced the pyrolysis process, and as the gas yield increased, the disorder of the resulting pyrolytic carbon also rose. The proposed Ni⁰-enhanced microwave pyrolysis mediated by nickel acetate offers a novel method for the efficient disposal and simultaneous resource recovery of waste textiles. Full article

Using agricultural waste biomass pyrolysis to produce energy sources and biochar may support local economies in rural areas and enhance sustainability in the agricultural sector, reducing dependence on traditional energy sources and fertilisers. To obtain liquid and gaseous forms of biomass fuel, wheat straw pellets were pyrolysed in a screw reactor at temperatures of 300, 400, 500, 600, and 700 °C. An analysis was conducted to assess the influence of process temperature on the physicochemical composition of the raw material and the resulting biochar, pyrolysis liquid, and synthesis gas. The presence of potentially harmful substances in the biochar, whose addition to soil can improve soil properties, was assessed by quantitatively determining polycyclic aromatic hydrocarbons (PAHs). Similar tests were carried out for pyrolysis fluid. The assessments were based on the standards for the most dangerous PAHs: fluorene, anthracene, fluoranthene, benzo[b]fluorine, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene. The results indicated that the total content of polycyclic aromatic hydrocarbons in the biochar ranged from 346.81 µg·kg⁻¹ at 300 °C to 1660.87 µg·kg⁻¹ (700 °C). In the pyrolytic fluid, the PAH content ranged from 58,240.7 µg·kg⁻¹ (300 °C) to 101,889.0 µg·kg⁻¹ (600 °C). It was found that the increase in PAH content in both the biochar and the liquid progressed with increasing pyrolysis temperature. After finding a correlation between the increase in the PAH content in biochar and the increase in the content of high-energy gases in the synthesis gas, it was concluded that it is difficult to reconcile the production of PAH-free biochar in the pyrolysis of biomass with obtaining high-energy gas and pyrolysis oil. Full article

Pharmaceutical packaging is one of the most used packaging types which contains aluminum and plastics. Due to increasing amounts of waste and rising environmental concerns, recycling approaches are being investigated. Since blisters usually contain a balanced amount of plastics and metals, most of the approaches focus on recycling only one material. Therefore, more sustainable recycling approaches which recover both plastic and aluminum fractions are needed. This study investigates the thermal behavior and degradation mechanisms of plastic-rich and aluminum-rich pharmaceutical blisters using various analytical techniques. Structural characterization revealed that plastic-rich blisters have a thicker profile with plastic and aluminum layers, while aluminum-rich blisters consist of plastic layers between aluminum sheets. Thermal degradation analysis showed two main stages for both types: plastic-rich blisters (polyvinyl chloride) exhibited significant weight loss and long-chain hydrocarbon formation between 210 and 285 °C, and aluminum-rich blisters (polyamide/nylon) degraded from 240 to 270 °C. Differential Scanning Calorimetry and Fourier Transform Infrared Spectroscopy analyses confirmed the endothermic behavior of such a transformation. The gas emissions analysis indicated an increased formation of gasses from the thermal treatment of plastic-rich blisters, with the presence of oxygen leading to the formation of carbon dioxide, water, and carbon monoxide. Thermal treatment with 5% O₂ in the carrier gas benefited plastic-rich blister treatment, reducing organic waste by up to 80% and minimizing burning risk, leveraging pyrolytic carbon for protection. This method is unsuitable for aluminum-rich blisters, requiring reduced oxygen or temperature to prevent pyrolytic carbon combustion and aluminum oxidation. Full article

This study evaluates the greenhouse gas (GHG) impacts of converting municipal solid waste (MSW) into methanol, focusing on both landfill methane (CH₄) emission avoidance and the provision of cleaner liquid fuels with lower carbon intensity. We conduct a life cycle assessment (LCA) to assess potential GHG reductions from MSW gasification to methanol, enhanced with hydrogen produced via natural gas pyrolysis or water electrolysis. Hydrogen enhancement effectively doubles the methanol yield from a given amount of MSW. Special attention is given to hydrogen production through natural gas pyrolysis due to its potential for lower-cost hydrogen and reduced reliance on renewable electricity compared to electrolytic hydrogen. Our analysis uses a case study of methanol production from an oxygen-fired entrained flow gasifier fed with refuse-derived fuel (RDF) simulated in Aspen HYSYS. The LCA incorporates the significant impact of landfill methane avoidance, particularly when considering the 20-year global warming potential (GWP). Based on the LCA, the process has illustrative net GHG emissions of 183 and 709 kgCO_2e/t MeOH using renewable electricity for electrolytic hydrogen and pyrolytic hydrogen, respectively, for the 100-year GWP. The net GHG emissions using 20-year GWP are −1222 and −434 kgCO_2e/t MeOH, respectively. Additionally, we analyze the sensitivity of net GHG emissions to varying levels of fugitive methane emissions. Full article