Search Results (457)

This study investigates the strengthening mechanisms of char in silicon dioxide thermal reduction through systematic high-temperature experiments using three char types (YQ1, CW1, HY1) characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and scanning electron microscopy. HY1 char demonstrated superior reactivity due to its highly ordered microcrystalline structure, characterized by the largest aromatic cluster size (L_a) and lowest defect ratio (I_D/I_G = 0.37), which directly correlated with enhanced reaction completeness. The carbon–silicon reaction reactivity increased progressively with temperature, achieving optimal performance at 1550 °C. Addition of Fe and Fe₂O₃ significantly accelerated the reduction process, with Fe₂O₃ exhibiting superior catalytic performance by reducing activation energy and optimizing reaction kinetics. The ferrosilicon formation mechanism proceeds through a two-stage pathway: initial char-SiO₂ reaction producing SiC and CO, followed by SiC–iron interaction generating FeSi, which catalytically promotes further reduction. These findings establish critical structure–performance relationships for char selection in industrial silicon production, where microcrystalline ordering emerges as the primary performance determinant. The identification of optimal temperature and additive conditions provides practical pathways to enhance energy efficiency and product quality in silicon metallurgy, enabling informed raw material selection and process optimization to reduce energy consumption and improve operational stability. Full article

The energetic valorization of digestate obtained from anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW) was investigated via pyrolysis in a bench-scale rotary kiln. The mass rate of dried digestate to the rotary kiln pyrolyzer was fixed at 500 gr/h. The effect of the pyrolysis temperature was investigated at 600, 700, and 800 °C. The pyrolysis products, char, oil, and gas, were quantified and chemically analyzed. It was observed that with the increase in the temperature from 600 to 800 °C, the char decreased from 60.3% to 52.2% and the gas increased from 26.5% to 35.3%. With the aim of increasing the methane production and methane concentration in syngas, the effect of CaO addition to the pyrolysis process was investigated at the same temperature, too. The mass ratio CaO/dried digestate was set at 0.2. The addition of CaO sorbent has a clear effect on the yield and composition of pyrolysis products. Under the experimental conditions, CaO was observed to act both as a CO₂ sorbent and as a catalyst, promoting cracking and reforming reactions of volatile compounds. In more detail, at the investigated temperatures, a net reduction in CO₂ concentration was observed in syngas, accompanied by an increase in CH₄ concentration. The gas yield decreased with the CaO addition because of CO₂ chemisorption. The oil yield decreased as well, probably because of the cracking and reforming effect of the CaO on the volatiles. A very promising performance of the CaO sorbent was observed at 600 °C; at this temperature, the CO₂ concentration decreased from 32.2 to 13.9 mol %, and the methane concentration increased from 16.1 to 29.4 mol %. At the same temperature, the methane production increased from 34 to 63 g/kg_digestate. Full article

Catalytic upgrading of pyrolysis oils is an important step for producing replacement hydrocarbon-rich liquid biofuels from biomass and can help to advance pyrolysis technology. Catalysts play a pivotal role in influencing the selectivity of chemical reactions leading to the formation of main compounds in the final upgraded liquid products. The present work involved a systematic study of solvent-free catalytic reactions of cyclohexanone in the presence of hydrogen gas at 160 °C for 3 h in a batch reactor. Cyclohexanone can be produced from biomass through the selective hydrogenation of lignin-derived phenolics. Three types of catalysts comprising undoped NbOPO₄, 10 wt% NiO/NbOPO₄, and 30 wt% NiO/NbOPO₄ were studied. Undoped NbOPO₄ promoted both aldol condensation and the dehydration of cyclohexanol, producing fused ring aromatic hydrocarbons and hard char. With 30 wt% NiO/NbOPO₄, extensive competitive hydrogenation of cyclohexanone to cyclohexanol was observed, along with the formation of C₆ cyclic hydrocarbons. When compared to NbOPO₄ and 30 wt% NiO/NbOPO₄, the use of 10 wt% NiO/NbOPO₄ produced superior selectivity towards bi-cycloalkanones (i.e., C₁₂) at cyclohexanone conversion of 66.8 ± 1.82%. Overall, the 10 wt% NiO/NbOPO₄ catalyst exhibited the best performance towards the production of precursor compounds that can be further hydrodeoxygenated into energy-dense aviation fuel hydrocarbons. Hence, the presence and loading of NiO was able to tune the activity and selectivity of NbOPO₄, thereby influencing the final products obtained from the same cyclohexanone feedstock. This study underscores the potential of lignin-derived pyrolysis oils as important renewable feedstocks for producing replacement hydrocarbon solvents or feedstocks and high-density sustainable liquid hydrocarbon fuels via sequential and selective catalytic upgrading. Full article

Halogenated flame retardants have been amongst the most widely used and effective solutions for enhancing fire resistance. However, their use is currently strictly regulated due to serious health and environmental concerns. In this context, phosphorus-based and mineral flame retardants have emerged as promising alternatives. Despite this, their combined use is neither straightforward nor guaranteed to be effective. This study scrutinizes the interactions between these two classes of flame retardants (FR) through a systematic analysis aimed at elucidating the antagonistic pathways that arise from their coexistence. Specifically, this study focuses on two inorganic fillers, mineral huntite and chemically precipitated magnesium hydroxide, both of which produce basic oxides upon thermal decomposition. These fillers were incorporated into a poly(butylene terephthalate) (PBT) matrix to be utilized as advanced-mattress FR coating fabric and were subjected to a series of flammability tests. The pyrolysis products of the prepared polymeric composite compounds were isolated and thoroughly characterized using a combination of analytical techniques. Thermogravimetric analysis (TGA) and differential thermogravimetric analysis (dTGA) were employed to monitor decomposition behavior, while the char residues collected at different pyrolysis stages were examined spectroscopically, using FTIR-ATR and Raman spectroscopy, to identify their structure and the chemical reactions that led to their formation. X-ray diffraction (XRD) experiments were also conducted to complement the spectroscopic findings in the chemical composition of the resulting char residues and to pinpoint the different species that constitute them. The morphological changes of the char’s structure were monitored by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Finally, the Limited Oxygen Index (LOI) and UL94 (vertical sample mode) methods were used to assess the relative flammability of the samples, revealing a significant drop in flame retardancy when both types of flame retardants are present. This reduction is attributed to the neutralization of acidic phosphorus species by the basic oxides generated during the decomposition of the basic inorganic fillers, as confirmed by the characterization techniques employed. These findings underscore the challenge of combining organophosphorus with popular flame-retardant classes such as mineral or basic metal flame retardants, offering insight into a key difficulty in formulating next-generation halogen-free flame-retardant composite coatings. Full article

To address the challenges of low density, loose structure, high utilization costs, and inadequate molding effects of corn straw char under ambient temperature and pressure conditions, this study investigated the utilization of waste soybean powder (WSP) as a binder to produce biochar pellets via ultrasonic-assisted processing. A single-factor experiment was initially conducted to assess the effects of key variables. Subsequently, a Central Composite Rotatable Design (CCRD) was employed to evaluate the individual and interactive effects of these variables, in which pellet density and durability served as response indicators. Regression models for both responses were developed and validated using analysis of variance (ANOVA). The results indicated that, at a 0.05 significance level, the mixing ratio of corn straw char to WSP and molding pressure had highly significant effects on pellet density, while pelleting time had a significant effect and ultrasonic power had no significant influence. All four factors significantly affected pellet durability, and their interactions were further analyzed. The optimal conditions were a mixing ratio of 45%, pelleting time of 33 s, an ultrasonic power of 150 W, and a molding pressure of 5 MPa, yielding pellets with a density of 1140.41 kg/m³ and a durability of 98.54%. These results demonstrate that WSP is an effective binder for the ultrasonic-assisted fabrication of biochar pellets. Full article

With the continuous reduction in fossil energy reserves and the increasingly prominent negative impacts on the environment, the search for sustainable alternative materials has become an urgent task. Biomass-based char has attracted much attention in the field of environmental protection, due to its wide-ranging and renewable raw materials. Hydrothermal carbonization and torrefaction carbonization, as two important biomass carbonization processes, each have their own advantages. This study focuses on the millions of tons of Chinese medicine residue waste generated in China every year. Four common Chinese medicine residues, Shanyao (Chinese yam), Suoyang (Cynomorium songaricum), Yujin (Curcuma aromatica), and Xueteng (Spatholobus suberectus), were selected and treated by hydrothermal carbonization and torrefaction carbonization processes at temperatures of 240 °C, 260 °C, and 280 °C. Through analysis techniques such as Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Scanning Electron Microscopy, the changes in the crystal structure, chemical functional groups, and microscopic morphology of the carbonized products were deeply studied, and the carbon yield was measured. The research aims to reveal the carbonization laws of Chinese medicine residues, provide a scientific basis for their efficient resource utilization, and help promote the development of biomass-based carbon materials in the field of environmentally friendly materials, alleviating energy and environmental pressures. Full article

Polyamide 6,6 (PA6,6) fabrics are widely used in textiles due to their high mechanical strength and chemical stability. However, their inherent flammability and melting behavior under fire pose significant safety challenges. In this study, a dual-layer flame-retardant system was developed by integrating atomic layer deposition (ALD) of ZnO with a phosphorus–silane-based flame retardant (DOPO-ETES). ALD allowed precise control of ZnO layer thickness (50, 84, and 199 nm), ensuring uniform coating. Thermal analysis (TGA) and microscale combustion calorimetry (MCC) revealed that ZnO altered the degradation pathway of PA6,6 through catalytic effects, promoting char formation and reducing heat release. The combination of ZnO and DOPO-ETES resulted in further reductions in heat release rates. However, direct flame tests showed that self-extinguishing behavior was not achieved, emphasizing the limitations related to the melting of PA6,6. TG-IR and cone calorimetry confirmed that ZnO coatings suppressed the release of smoke-related volatiles and incomplete combustion products. These findings highlight the potential of combining metal-based catalytic flame retardants like ZnO with phosphorus-based coatings to improve flame retardancy while addressing the specific challenges of polyamide textiles. This approach may also be adapted to other fabric types and integrated with additional flame retardants, broadening its relevance for textile applications. Full article

This study explored the production and activation of biochar from rice straw residue for dye adsorption applications. Rice straw, a widely available but underutilized biomass, was processed to isolate lignin and generate biochar through pyrolysis at 450 °C and 550 °C. Activation using chemical agents (e.g., KOH and NaOH) was performed to enhance surface area and porosity. Among the tested conditions, KOH activation at a char-to-agent ratio of 1:3 produced activated carbon at 800 °C with the highest BET surface area (835.2 m²/g), and high fixed carbon (44.4%) after HCl washing. Thermogravimetric analysis was used to investigate pyrolysis kinetics, with activation energies determined using the Kissinger, Flynn–Wall–Ozawa, and Kissinger–Akahira–Sunose models. The brown solid showed a higher activation energy (264 kJ/mol) compared to isolated lignin (194 kJ/mol), indicating that more energy is required for decomposition. The AC was evaluated for the adsorption of methylene blue (MB) and methyl orange (MO) from aqueous solutions. Both dyes followed the Langmuir isotherm model, indicating that monolayer adsorption occurred. The maximum adsorption capacities reached 222 mg/g for MB and 244 mg/g for MO at 303 K, with higher values at elevated temperatures. Adsorption followed a pseudo-second-order kinetic model and was governed by a physisorption mechanism, as supported by thermodynamic analysis (ΔH < 20 kJ/mol and E_a < 40 kJ/mol). These findings demonstrate that KOH-activated biochar from rice straw residue is a high-performance, low-cost adsorbent for dye removal, contributing to sustainable biomass utilization and wastewater treatment. Full article

The thermal resistance of carbon fiber–reinforced poly(phenylene sulfide) to harsh oxidative conditions is investigated through thermogravimetric experiments performed in an oxygen atmosphere. While these materials usually show great resistance against thermal decomposition in a nitrogen atmosphere, the experiments in oxygen reveal the total decomposition of both the matrix and the carbon fibers. The Gram–Schmidt signal, obtained by coupling thermogravimetric analysis in standard conditions with Fourier-transform infrared spectroscopy, exhibits multiple events, evidencing that the decomposition proceeds through distinct stages. The first step characterizes the char formation, while the second relates to its oxidative decomposition. A third step, only observed for composites, is interpreted as the signature of the oxidative decomposition of carbon fibers. To mimic the sudden elevation of temperature encountered during a fire, the analyses are performed at rates of up to 500 K min⁻¹. These specific experimental conditions reveal a complex dependence of the thermogravimetric signature on the heating rate. Independent of the atmosphere, nitrogen or oxygen, the characteristic temperature of decomposition follows a bell-shape trend, resulting from the combination of lag effects and thermal-conductivity limitations. Additionally, the increase of the heating rate causes the Gram–Schmidt signal to evolve toward a broad peak with indistinct events. To investigate whether these changes affect the decomposition products, the infrared spectra, continuously recorded to probe the whole decomposition, are compared with those from the database. The char formation is characterized by the production of sulfur dioxide, while carbon dioxide is the main product emitted during both char and fiber oxidative decomposition. Owing to the merging of the decomposition stages, sulfur-dioxide detection is partly supplanted by that of carbon dioxide under fast elevations of temperature. Full article

To ensure agricultural safety and ecological security, it is crucial to effectively immobilize emerging organic pollutants, such as plasticizers, to prevent their migration in various environmental matrices. However, the ideal immobilization agent with the advantages of being environmentally friendly is very rare. In this study, low-cost and stable near-natural immobilization agents, char-derived artificial humic acids, CHAs, were proposed and prepared via hydrothermal humification (180 °C) and pyrolysis (300, 500, or 700 °C) of agroforestry biowaste. The resulting CHAs exhibit high purity (composed primarily of C (67.28–81.35%), O (6.65–21.64%), H (1.40–5.28%), and N (0.36–0.58%)) with remarkably low ash content (5.43–10.02%). Characterization revealed a compact structure with a limited porosity with small surface area (0.27–0.32 m² g⁻¹) and pore volume (2.99–3.43 × 10⁻⁴ cm³ g⁻¹). Notably, high-temperature pyrolysis induced consumption of oxygen-containing functional groups while promoting aromatic structure formation. The sorption behavior of diethyl phthalate, a representative plasticizer, on CHAs was well described by both Langmuir isotherm and pseudo-second-order kinetic models. The CHAs exhibited remarkable sorption performance for diethyl phthalate, with a maximum sorption capacity reaching 3345 mg kg⁻¹ as determined by the Langmuir model. The sorption of diethyl phthalate onto CHAs is mainly multi-layer sorption dominated by physical processes, mainly including pore filling, partitioning, hydrogen bonding, and π–π stacking. Mean sorption energies ranging from 2.56 to 4.99 × 10⁻³ kJ mol⁻¹ indicate the predominance of physical sorption mechanisms. This study developed a method to convert the liquid by-product produced during hydrothermal humification of biowaste into stable near-natural and carbon-rich char materials, and the proposed materials show great promise in immobilizing pollutants from various environmental matrices. Full article

This study employed a two-stage fixed-bed pyrolysis-reforming reactor to investigate H₂ production behaviors from municipal solid waste (MSW) and biomass with their self-derived catalysts under different operating parameters. The self-derived catalysts are prepared by mechanically mixing pyrolysis-derived chars with CaO and iron powders. The main results are as follows: (1) The higher oxygen content in biomass facilitates oxidative dehydrogenation reactions, enabling in situ generation of H₂O, which results in a higher H₂/CO ratio for biomass compared to MSW under steam-free conditions. (2) There are optimal values for the reforming temperature and steam-to-feedstock ratio (S/F) to achieve best performance. In the presence of steam, MSW generally exhibits superior H₂ and syngas production performance to biomass; (3) Both MSW char (MSWC)- and biomass char (BC)-based catalysts showed satisfied H₂ production and tar cracking performance at 850–900 °C, and the MSWC-based catalyst demonstrated better catalytic activity than the BC-based catalyst due to its higher contents of several active metals. In addition, the iron powder can be recycled easily, proving the effectiveness of the self-derived convenient and cheap catalysts. Full article

To promote renewable energy sources, we focus on optimizing the design of solar–biomass pyrolysis systems. This study suggests the best reactor orientation that creates effective thermal–solar systems for pyrolysis. Solar–biomass pyrolysis uses solar energy to create valuable products like syngas, tar, and char from biomass. This process promotes energy sustainability. We analyze different solar reactors based on their design, operation, heat transfer rate, efficiency, residence time for biomass retention inside the reactor, and biomass conversion efficiency. A thorough analysis of the existing technologies helps to pinpoint the difficulties and most recent developments in the sector, making decision making more manageable and providing information on the viability and sustainability of biomass conversion technologies. Full article

This research delves into the co-pyrolysis of refuse-derived fuel (RDF) and oil shale (OS), utilizing a 50% weight ratio for each component. The study employs a fixed-bed reactor, augmented by electrical kiln heating, to conduct the co-pyrolysis process. A significant aspect of this research is the use of Aspen Plus software for process simulation, with the simulated results undergoing validation through experimental data. A commendable correlation was observed between the experimental outcomes and the model predictions, underscoring the reliability of the simulation approach. The investigation reveals distinct product yields from the pyrolysis of 100% RDF and 100% OS. Specifically, the pyrolysis of pure RDF yielded 45.26% gas, 20.67% oil, and 34.07% char by weight. In contrast, the pyrolysis of pure OS resulted in 14.51% gas, 8.32% liquid, and a significant 77.61% char by weight. The co-pyrolysis of RDF and OS in a 50% blend altered the product distribution to 31.98% gas, 12.58% liquid, and 55.09% char by weight. Furthermore, the Aspen Plus simulation model aligned closely with these findings, predicting yields of 31.40% gas, 11.9% oil, and 56.6% char by weight for the RDF-OS blend. This study not only elucidates the co-pyrolysis behavior of RDF and OS but also contributes valuable insights into the potential of these materials to address the pressing issue of plastic waste management and energy resource utilization. The findings underscore the efficacy of RDF and OS co-pyrolysis as a viable strategy for enhancing the value extraction from waste and underutilized energy resources, presenting a promising avenue for environmental and energy sustainability. Full article

The pyrolysis of non-recyclable construction, renovation, and demolition (CRD) wood waste is a complex thermochemical process involving devolatilization, diffusion, phase transitions, and char formation. CRD wood, a low-ash biomass containing 24–32% lignin, includes both hardwood and softwood components, making it a viable heterogeneous feedstock for bioenergy production. Thermogravimetric analysis (TGA) of CRD wood residues was conducted at heating rates of 10, 20, 30, and 40 °C/min up to 900 °C, employing model-fitting (Coats–Redfern (CR)) and model-free (Ozawa–Flynn–Wall (OFW), Kissinger–Akahira–Sunose (KAS), and Friedman (FM)) approaches to determine kinetic and thermodynamic parameters. The degradation process exhibited three stages, with peak weight loss occurring at 350–400 °C. The Coats–Redfern method identified diffusion and phase interfacial models as highly correlated (R² > 0.99), with peak activation energy (E_a) at 30 °C/min reaching 114.96 kJ/mol. Model-free methods yielded E_a values between 172 and 196 kJ/mol across conversion rates (α) of 0.2–0.8. Thermodynamic parameters showed enthalpy (ΔH) of 179–192 kJ/mol, Gibbs free energy (ΔG) of 215–275 kJ/mol, and entropy (ΔS) between −60 and −130 J/mol·K, indicating an endothermic, non-spontaneous process. These results support CRD wood’s potential for biochar production through controlled pyrolysis. Full article

This study systematically examines the effect of the morphology of cerium oxide (CeO₂) on the flame retardancy, thermal stability, and mechanical properties of polypropylene composites with intumescent flame retardant (PP/IFR). Layer-CeO₂ (L-CeO₂) outperforms Particulate-CeO₂ (P-CeO₂) in enhancing the flame retardancy of PP/IFR composites, showing higher limiting oxygen index (LOI) and greater reductions in the total heat release rate (THR) and total smoke production (TSR). The substitution of 1% IFR with 1% L-CeO₂ significantly increased the LOI from 29.4% to 32.6%, while reducing the THR and TSR by 38.9% and 74.3%, respectively. L-CeO₂ incorporation improves thermal stability, increasing the residual char yield to 8.53% at 800 °C under air (vs. 3.87% for PP/IFR). Additionally, L-CeO₂ improved the mechanical properties of the composites, increasing tensile strength and rigidity. The synergistic flame-retardant mechanism is hypothesized to involve CeO₂ catalyzing the formation of a P-O-C crosslinked network in the carbon layer, leading to a denser carbon structure and improved flame-retardant performance in the PP/IFR composites. These findings demonstrate the efficacy of L-CeO₂ as a flame-retardant synergist, providing a foundation for developing fire-safe polymeric materials. Full article