Effects of biomass co-pyrolysis and herbaceous plant colonization on the transformation of tailings into soil like substrate.

Enhancing soil organic matter characteristics, ameliorating physical structure, mitigating heavy metal toxicity, and hastening mineral weathering processes are crucial approaches to accomplish the transition of tailings substrate to a soil-like substrate. The incorporation of biomass co-pyrolysis and plant colonization has been established to be a significant factor in soil substrate formation and soil pollutant remediation. Despite this, there is presently an absence of research efforts aimed at synergistically utilizing these two technologies to expedite the process of mining tailings soil substrate formation. The current study aimed to investigate the underlying mechanism of geochemical changes and rapid mineral weathering during the process of transforming tailings substrate into a soil-like substrate, under the combined effects of biomass co-smoldering pyrolysis and plant colonization. The findings of this study suggest that the incorporation of smoldering pyrolysis and plant colonization induces a high-temperature effect and biological effects, which enhance the physical and chemical properties of tailings, while simultaneously accelerating the rate of mineral weathering. Notable improvements include the amelioration of extreme pH levels, nutrient enrichment, the formation of aggregates, and an increase in enzyme activity, all of which collectively demonstrate the successful attainment of tailings substrate reconstruction. Evidence of the accelerated weathering was verified by phase and surface morphology analysis using X-ray diffraction and scanning electron microscopy. Discovered corrosion and fragmentation on the surface of minerals. The weathering resulted in corrosion and fragmentation of the surface of the treated mineral. This study confirms that co-smoldering pyrolysis of biomass, combined with plant colonization, can effectively promote the transformation of tailings into soil-like substrates. This method has can effectively address the key challenges that have previously hindered sustainable development of the mining industry and provides a novel approach for ecological restoration of tailings deposits.

Oxygen atmosphere enhances ball milling remediation of petroleum-contaminated soil and reuse as adsorptive/catalytic materials for wastewater treatment.

Ball milling is an environmentally friendly technology for the remediation of petroleum-contaminated soil (PCS), but the cleanup of organic pollutants requires a long time, and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume. The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil (BCS-O) as wastewater treatment materials. The total petroleum hydrocarbon removal rates by ball milling under vacuum, air, and oxygen atmospheres are 39.83%, 55.21%, and 93.84%, respectively. The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals. The Cu2+, Ni2+, and Mn2+ adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides. Furthermore, BCS-O can effectively activate persulfate (PDS) oxidation to degrade aniline, while BCS-O loaded with transition metal (BCS-O-Me) shows better activation efficiency and reusability. BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by 1O2 oxidation and electron transfer. The main active sites are oxygen-containing functional groups, vacancy defects, and graphitized carbon. The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate 1O2 and attack aniline. Graphitized carbon promotes aniline degradation by accelerating electron transfer. The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the post-remediation soil.

Quantitative determination of olefins in pyrolysis oils from waste plastics and tires using selective adsorption by Ag-SiO2 followed by GC×GC-FID.

Determination of olefins in pyrolysis oils from waste plastics and tires is crucial for optimizing the pyrolysis process and especially for the further advanced valorization of these oils in terms of the circular economy. Identifying olefins, even using high-resolution techniques like GC×GC, is challenging without TOF-MS, which allows modification of the ionization step. Currently, the only method for determining olefins in plastic pyrolysis oils is GC-VUV, recently standardized as ASTM D8519. However, TOF-MS and VUV are not affordable instruments for many research teams working on plastics recycling. This paper introduces a simple method for the selective micro-scale adsorption of olefins over AgNO3/SiO2, followed by the GC×GC-FID analysis. Olefins are determined indirectly from the loss of chromatographic area in respective hydrocarbon groups before and after removal. Only 50 µL sample and 15 min of sample separation are needed. Our method was extensively validated and provides a reliable determination of olefin content in a wide range of pyrolysis oils from plastics and tires and their products after mild hydrotreatment. It is affordable to all researchers and industrial companies working on plastics recycling by thermochemical processes as it does not require an MS detector.

Catalytic Pyrolysis of Polyethylene with Microporous and Mesoporous Materials: Assessing Performance and Mechanistic Understanding.

Testing the performance for the catalytic pyrolysis of plastic waste is hampered by mass transfer limitations induced by a size mismatch between the catalyst's pores and the bulky polymer molecules. To investigate this aspect, the behavior of a series of microporous and mesoporous materials was assessed in the catalytic pyrolysis of polyethylene (PE). More specifically, a mesoporous material, namely sulfated zirconia (Zr(SO4)2) on SBA-15, was synthesized to increase the pore accessibility, which reduces mass transfer limitations and thereby enables to better assess the effect of active site density. To demonstrate this approach, mesoporous SBA-15 was compared to microporous zeolite Y. Using the degradation temperature during thermogravimetric analysis as a measure of activity, no correlation between acidity and activity was observed for microporous zeolite Y. However, depending on the Mw of PE, the reactivity of the mesoporous catalysts increased with increasing Zr(SO4)2 weight loading, showing that utilizing a mesoporous catalyst can overcome the accessibility limitations at least partially, which was further confirmed by polymer melt infiltration and in situ X-ray diffraction. Product analysis revealed that more aromatics and coke were produced with zeolite Y. The mesoporous material remained active and structurally intact and catalyses PE degradation via acid- and radical-based pathways.

A critical review on emerging industrial applications of chars from thermal treatment of biosolids.

Thermochemical treatment is rapidly emerging as an alternative method for the management of stabilised sewage sludges (biosolids) to effectively reduce waste volume, degrade contaminants, and generate valuable products, particularly biochar and hydrochar. Biosolids-derived char has a relatively high concentration of heavy metals compared with agricultural chars but is still applied to land due to its beneficial properties and ability to retain metals. However, non-agricultural applications can provide additional economic and environmental benefits, promote sustainability and support a circular economy. This review identifies extensive non-agricultural opportunity for biosolids biochar, including adsorption, catalysis, energy storage systems, biological process enhancement, and as additives for rubber compounding and construction. Biosolids chars have received limited attention vs agricultural char, and we draw on both areas of literature, as well as evaluating differences between agricultural and biosolids chars. A key opportunity for biosolids biochar in comparison with other materials and agricultural chars is its sustainable and low-cost nature, relatively high metals content, improving catalyst properties, and ability to modify in various stages to tune it to specific applications. The specific opportunities for hydrochar have only received limited attention. Research needs to include better understanding of the benefits and limitations for specific applications, as well as adjacent drivers, including society, regulation, and market and economics.

Pyrolysis-induced migration and transformation of heavy metals in sewage sludge containing microplastics.

Stabilizing heavy metals (HMs) in sewage sludge is urgently needed to facilitate its recycling and reuse. Pyrolysis stands out as a promising method for not only stabilizing these metals but also producing biochar. Our research delves into the migration and transformation of specific HMs (Cr, Mn, Ni, Cu, Zn, As, and Pb) during co-pyrolysis under various conditions, including the presence and absence of microplastics (PVC and PET). We examined different concentrations of these plastics (1 %, 5 %, 10 %, and 15 %) and temperatures (300 °C, 500 °C, and 700 °C). Findings reveal that microplastics, particularly PVC, enhance the migration of Zn and Mn, leading to significant volatilization of Zn and Pb at higher temperatures, peaking at 700 °C. The increase in temperature also markedly influences HM migration, with As showcasing notable loss rates that climbed by 18.0 % and 16.3 % in systems with PET and PVC, respectively, as temperatures soared from 300 °C to 700 °C. Moreover, our speciation analysis indicates that microplastics aid in transforming certain HMs from unstable to more stable forms, suggesting their beneficial role in HM stabilization during pyrolysis. This study significantly enriches our understanding of microplastics' impact on HM behavior in sewage sludge pyrolysis, offering new avenues for pollution control and environmental management strategies.

Wood biochar induced metal tolerance in Maize (Zea mays L.) plants under heavy metal stress.

Due to metal toxicity, widespread industrialization has negatively impacted crop yield and soil quality. The current study was aimed to prepare and characterize biochar made from wood shavings of Pinus roxburghii and to determine the plant growth promoting and heavy metal detoxification of cadmium (Cd) and chromium (Cr) contaminated soil. FTIR SEM coupled with EDX characterization of biochar was performed; Cd and Cr were used at a rate of 20 mg/kg. Biochar was used at the rate of 50 mg/kg for various treatments. The completely randomized design (CRD) was used for the experiment and three replicates of each treatment were made. Various agronomic and enzymatic parameters were determined. The results indicated that all growth and enzymatic parameters were enhanced by the prepared biochar treatments. The most prominent results were observed in treatment T5 (in which shoot length, root length, peroxidase dismutase (POD), superoxide dismutase (SOD) catalyzes (CAT), and chlorophyll a and b increased by 28%, 23%, 40%, 41%, 42%, and 27%, respectively, compared to the control). This study demonstrated that biochar is a sustainable and cost-effective approach for the remediation of heavy metals, and plays a role in plant growth promotion. Farmers may benefit from the current findings, as prepared biochar is easier to deliver and more affordable than chemical fertilizers. Future research could clarify how to use biochar optimally, applying the minimum amount necessary while maximizing its benefits and increasing yield.

Regulation of Ir Dopant in Mo Oxides by Flame Spray Pyrolysis for Efficient CO2 Hydrogenation.

Mo carbide is recognized as one of the most promising catalyst for CO2 utilization via reverse water-gas shift (RWGS). However, it always suffered from low processing capacity, undesired products and deactivation. Herein, an Ir modified MoO3 synthesized by the flame spray pyrolysis (FSP) method exhibits higher reaction rate (63.0 gCO2·gcat-1·h-1) compared to the one made by traditional impregnation method (45.8 gCO2·gcat-1·h-1) over the RWGS reaction at 600°C. The distinguishing feature between the two catalysts lies in the chemical state and space distribution of Ir species. Ir species predominated in the bulk phase of MoO3 during the quenching process of the FSP method and were mainly in the metallic states, which revealed by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) characterizations. In contrast, the Ir introduced via impregnation method were mainly on the surface of MoO3 and in oxidized state. The regulation of Ir dopant in MoO3 catalyst by different methods determines the carbonization process to Mo carbides, and thus affects the catalytic performance. This work sheds light on the superiority of the FSP method in synthesizing Mo oxides with heteroatoms and further creating an efficient Mo-based catalyst for CO2 conversion.

Facile synthesis of ZnO nanoparticles using Nigella Sativa extract and its role as catalyst in production of bio-oil and degradation of methylene blue dye.

Zinc Oxide (ZnO) nanoparticles (NPs) were synthesized using an environmentally benign biogenic approach employing an extract of kernels of Nigella Sativa (kalonji). The presence of primary and secondary metabolites in Nigella Sativa extract acted as the capping and reducing agent. The as-synthesized ZnO NPs were characterized using various advanced techniques i.e., UV, SEM, XRD, EDS, TGA, DSC, and FTIR spectra. UV characterization of ZnO NPs revealed a peak within the 350-400 cm-1 range, confirming their successful formation. XRD spectra revealed that the particles possess a nano-rods and platelets structure, with an average size of 65 nm. XRD analysis revealed that the particles possess a size of 65 nm with a nano-rods and platelets structure. FTIR spectra of the ZnO NPs exhibited a peak at a wavenumber range of 500-600 cm-1. The newly fabricated ZnO NPs were utilized in a pyrolysis reaction for the production of high-yield bio-oil, resulting in a maximum yield of 65.6 % at 350 °C. The spectra of the bio-oil display distinct peaks at 1340 cm-1, 2923.6 cm-1, and 1617 cm-1, which suggest the existence of phenolic and carbonyl chemicals. After incubating for 24 h under UV light, they also demonstrated significant catalytic degradation of methylene blue dye. The highest degradation was recorded to be an average of 71 % in 60 min of UV exposure. Taken together, ZnO NPs developed by eco-benign methods have the potential to be implemented as a novel catalytic system in the production of bio-oil as well as the remediation of dye-harboring industrial wastewater.

TG-FTIR-Py-GCMS analysis and catalytic pyrolysis mechanism of textile waste by red mud catalyst for liquid fuel production.

The substantial generation of textile waste (TW) and red mud (RM) has resulted in significant resource wastage and environmental challenges. Co-utilization technology of solid waste is an effective approach to improve waste utilization efficiency. In this study, RM catalytic pyrolysis experiments of TW were conducted using TG-FTIR and Py-GC-MS for liquid fuel production, and TW and RM were recycled simultaneously. At the optimal experimental conditions (temperature of 600 °C and feed catalyst ratio of 2:1), the tar yield and higher heating value (HHV) of TW pyrolysis catalyzed by RM were 73.43 wt% and 32.34 kJ/g, respectively. Additionally, experiments on the pyrolysis of various TW types revealed that LDPE and PP are suitable for tar production, while cotton, nylon, and PET are more suitable as feedstock for syngas production. The RM catalytic pyrolysis mechanism of textile waste is that Fe2O3 in RM exhibits significant catalytic activity in enhancing tar and syngas yields. However, during the catalytic process, Fe2O3 undergoes reduction to Fe3O4, resulting in diminished catalytic performance of the RM. After five cycles of use, the RM essentially lost its catalytic activity due to the accumulation of char and tar. All experimental findings of this study could offer an effective guideline for TW recycle and promoting RM utilization toward the waste-to-energy circular economy.

Investigation of kinetics, reaction mechanisms, thermodynamics, and synergetic effects in co-pyrolysis of wood sawdust and linear low-density polyethylene using the thermogravimetric approach.

This study focused on investigating thermal degradation behaviors, kinetics, reaction mechanisms, synergistic effects, and thermodynamic parameters of wood sawdust (WSD), linear low-density polyethylene (LLDPE), and their blends (LW1:3, LW1:1, and LW3:1) during co-pyrolysis in a thermogravimetric analyzer (TGA). Thermal behavior exhibited a LW1:3 blend (25 wt.% LLDPE) showing significant mass loss at lower temperatures (150 to 300 °C) compared to the individual feedstocks, such as 150 to 400 °C and 300 to 520 °C for WSD and LLDPE, respectively. The iso-conversional methods (KAS, FWO, and FM) were used to determine the kinetic parameters (Ea and A), and the activation energy drop was highest for the LW1:3 blend. According to the master plots, the third-order reaction (O3), nucleation (P2/3), and diffusional model (D4) were the predominant reaction mechanisms for the co-pyrolysis of the LW1:3, LW1:1, and LW3:1 blend, respectively. The thermodynamic parameters demonstrate that a small amount of plastic addition into WSD can improve the reactivity of the blend, shorten the reaction time, and cause less energy-intensive reactions. The values of ΔH, ΔG, and ΔS also confirmed the co-pyrolysis process's spontaneity and endothermic nature. The Fourier transforms infrared spectrometer (FTIR) spectra of raw feedstock, blends, and their biochar revealed some of the peaks were shifted, the intensity was reduced, and disappearance can happen when the temperature was increased. Using the experimental and theoretical/predicted activation energies, the parity chart illustrates the synergistic effects of co-pyrolysis of different blends, and the LW1:3 blend has a favorable synergistic impact. These results could be helpful in process optimization and designing an effective reactor system for co-pyrolysis.

Pyrolytic conversion of glucose into hydroxymethylfurfural and furfural: Benchmark quantum-chemical calculations.

Quantum chemical methods have been intensively applied to study the pyrolytic conversion of glucose into hydroxymethylfurfural (HMF) and furfural (FF). Herein, we collect the most relevant mechanistic proposals from the recent literature and organize them into a single reaction network. All the transition structures (TSs) and intermediates are characterized using highly accurate ab initio methods and the possible reaction pathways are assessed in terms of the Gibbs energies of the TSs and intermediates with respect to ß-glucopyranose, selecting a 2D ideal-gas standard state at 773 K to represent the pyrolysis conditions. Several pathways can lead to the formation of both HMF and FF passing through rate-determining TSs that have ΔG‡ values of ~49-50 kcal/mol. Both water-assisted mechanisms and nonspecific environmental effects have a minor impact on the Gibbs energy profiles. We find that the HMF → FF + CH2O fragmentation has a small ΔrxnG value and an accessible ΔG‡ barrier. Our computational results, which are in consonance with the kinetic parameters derived from lumped models, the results of isotopic labeling experiments and the reported HMF/FF molecular ratios, could be useful for modeling studies including on nonequilibrium kinetic effects that may render more information about product yields and the relevance of the various pathways.

Thermal and Catalytic Recycling of Plastics from Waste Electrical and Electronic Equipment-Challenges and Perspectives.

The amount of end-of-life electrical and electronic devices has been widely increased, globally. This emphasizes how recycling waste electric and electronic equipment (WEEE) is essential in order to reduce the amount of WEEE that is disposed of directly in the environment. Plastics account for a big percentage in WEEE, almost 20%. As a result, the application of recycling methods on plastics gathered from WEEE is of great importance since, in this way, landfill disposal can be reduced. Nevertheless, despite the advantages, there are a lot of difficulties, such as the variety of different plastics present in the plastic mix and the existence of various additives in the plastic parts, for instance, brominated flame retardants that need special attention during their treatments, which restricts their wide application. Considering all these, this review aims to provide readers with all the current techniques and perspectives that are available for both the thermal and the catalytic recycling of plastics retrieved from WEEE. Apart from the up-to-date information on the recycling methods, in this review, emphasis is also given on the advantages each method offers and also on the difficulties and the limitations that may prevent them from being applied on a large scale. Current challenges are critically examined, including the use of mechanical or thermo-chemical recycling, the treatment of individual polymers or polymer blends and the separation of harmful additives before recycling or not. Finally, emerging technologies are briefly discussed.

Molecular Dynamics Simulations Guide the Gasification Process of Carbon-Supported Nickel Catalysts in Biomass Supercritical Water.

In this study, the Density Functional Theory (DFT) Calculations for Molecules and Clusters-ADF module is employed to model carbon-supported nickel catalysts and lignin monomers, integrating the ReaxFF module to simulate molecular dynamics under supercritical water conditions, with a focus on lignin decomposition reactions. Molecular dynamics models for supercritical water gasification are established under various conditions such as catalyst presence, water molecule quantities, and reaction temperature. By comparing simulation systems under different conditions, the yields of and variations in combustible gases (hydrogen and carbon monoxide) are summarized. Introducing heteroatoms into the lattice of the carbon support can alter the electronic structure within graphene, thereby influencing its electrical and electrochemical properties, increasing the number of active sites, and significantly enhancing electrocatalytic activity. Simulation results indicate that carbon-supported nickel metal catalysts can promote the cleavage of C-C bonds in lignin monomers, thereby increasing the rate of water-gas shift reactions and boosting hydrogen production in the system by 105%. Increasing water molecule quantities favored water-gas shift reactions and hydrogen generation while lowering carbon monoxide formation. Moreover, elevating reaction temperatures led to increased hydrogen and carbon monoxide production rates, which were particularly pronounced between 2500 K and 3500 K. These findings offer crucial theoretical insights for advancing efficient hydrogen production through biomass supercritical water gasification.

Investigation on the Curing and Thermal Properties of Epoxy/Amine/Phthalonitrile Blend.

The bisphenol A-type phthalonitrile (BAPH) was blended with the classic epoxy system E51/DDS to prepare the epoxy/phthalonitrile thermoset. The curing kinetics were investigated by differential scanning calorimetry (DSC) using the isoconversional principle, and the average activation energy (Eα) of the E51/DDS curing reaction was found to decrease from 87 kJ/mol to 68.6 kJ/mol. Combining the results of the rheological study, the promoting effect of phthalonitrile on the crosslink of epoxy/amine is confirmed. The curing reaction of the blended resin was characterized using FTIR, and the results showed that BAPH could react with DDS. The thermal behaviors of the thermosets were investigated via DMA and TGA. The glass transition temperature (Tg) is found to increase from 181 °C to 195 °C. The char yield increases from 16% to 59.6% at 800 °C in a N2 atmosphere, which is higher than the calculated value based on the proportional principle. The AFM phase images show that there is no phase separation in the cured thermoset. The results imply that the cured epoxy/amine/phthalonitrile blend is probably a kind of copolymer. The real-time TG-MS indicated that the pyrolysis of the thermoset can be divided into two relatively independent stages, which can be assigned to the cleavage of the E51/DDS network, and the phthalocyanine/triazine/isoindoline, respectively.

Insights into the Synergistic Effect and Inhibition Mechanism of Composite Conditioner on Sulfur-Containing Gases during Sewage Sludge Pyrolysis.

Sewage sludge odorous gas release is a key barrier to resource utilization, and conditioners can mitigate the release of sulfur-containing gases. The gas release characteristics and sulfur compound distribution in pyrolysis products under both single and composite conditioning strategies of CaO, Fe2O3, and FeCl3 were investigated. This study focused on the inhibition mechanisms of these conditioners on sulfur-containing gas emissions and compared the theoretical and experimental sulfur content in the products to evaluate the potential synergistic effects of the composite conditioners. The findings indicated that at 650 °C, CaO, Fe2O3, and FeCl3 inhibited H2S release by 35.8%, 23.2%, and 9.1%, respectively. Notably, the composite of CaO with FeCl3 at temperatures ranging from 350 to 450 °C and the combination of Fe2O3 with FeCl3 at 650 °C were found to exert synergistic suppression on H2S emissions. The strongly alkaline CaO inhibited the metathesis reaction between HCl, a decomposition product of FeCl3, and the sulfur-containing compounds within the sewage sludge, thereby exerting a synergistic suppression on the emission of H2S. Conversely, at temperatures exceeding 550 °C, the formation of Ca-Fe compounds, such as FeCa2O4, appeared to diminish the sulfur-fixing capacity of the conditioners, resulting in increased H2S emissions. For instance, the combination of CaO and FeCl3 at 450 °C was found to synergistically reduce H2S emissions by 56.3%, while the combination of CaO and Fe2O3 at 650 °C synergistically enhances the release of H2S by 23.6%. The insights gained from this study are instrumental in optimizing the pyrolysis of sewage sludge, aiming to minimize its environmental footprint and enhance the efficiency of resource recovery.

Life cycle assessment of recycling metallised food packaging plastics using mechanical, thermal and chemical processes.

Single treatment of metallised food packaging plastics waste (MFPW) has shown disappointing results with recycling rate <20 % due to its complex structure consisting of 10 % aluminium (Al) and 90 % mixed plastic films made of PE, PP, PS, PET, etc. Besides, it is generating many emissions and residues that must be landfilled making it difficult to integrate them into the circular economy. Therefore, a multi-stage recycling (MSR) approach has recently been developed using several sequential mechanical, thermal and chemical processes to recover energy and Al from MFPW with additional revenue for recycling plant operators. The thermal treatment helps to decompose the plastic fraction into wax or oil, gaseous, and solid residue (SR) composed of Al and coal, while the mechanical process can be used as a pre-treatment of MFPW feedstock and SR. Finally, the chemical treatment (leaching and functionalization) can be used to extract Al from SR and to refine coal into carbon microparticles (CPs), respectively. In order to investigate the environmental performance of the proposed MSR system, this research was developed. The investigation was performed using SimaPro life cycle analysis (LCA) tool according to ISO 14040/44 Standards and the impact assessment method is ReCiPe 2016. Five different scenarios were proposed in the constructed LCA layout, namely, conversion of MFPW to a) wax and gas (pyrolysis), b) wax, gas, and aluminium chloride (AlCl3) (pyrolysis and leaching), c) wax, gas, AlCl3, and CPs (pyrolysis, leaching, and functionalization), and d) oil, gas, AlCl3, and CPs (catalytic pyrolysis, leaching, and functionalization). Besides, the oil produced from catalytic pyrolysis is used for generation of electricity (scenario e). The results showed that wax and gas recovery scenario (a) has better environmental potential and environmental benefits compared to incineration practice. The results did not change much after extraction of Al and CPs (scenario b, c), with a few increasing by 2-4% in the total score. While a lot of environmental burdens from upgrading and utilization (Scenario d, e) were recorded, reaching 79 % due to the huge amount of the catalyst was used. Thus, MSR systems have bigger environmental benefits, however, the chemical and catalytic processes still need to be further improved to reduce the effect of terrestrial acidification.

Pyrolysis kinetics of waste ryegrass under nitrogen and air atmosphere.

To investigate the pyrolysis reaction of ryegrass, we conducted a simultaneous thermal analysis using thermogravimetric(TG) analyzers. This involved obtaining data through Thermogravimetry (TG), Derivative Thermogravimetry (DTG), and Differential thermal analysis (DTA) techniques. The experiments were conducted under dynamic nitrogen and air atmospheres at different heating rates. The kinetic parameters of ryegrass pyrolysis were determined using the Kissinger method, the Flynn-Wall-Ozawa (FWO) peak conversion rate approximate equivalence method, the Flynn-Wall-Ozawa (FWO) equal conversion rate method, and the Skvára-Sesták (S-S) method. It provides a theoretical basis for the reuse of ryegrass resources. The findings indicated that the pyrolysis temperature of ryegrass increased with the accelerated rate of temperature increase in both atmospheres. The average weight loss rate of pyrolysis of ryegrass in the air atmosphere (92.27 %) is higher than that compared to that in a nitrogen atmosphere (86.11 %). Additionally, the temperature required for complete decomposition is lower in the former case. The FWO peak conversion rate approximation equivalence approach and the FWO equal conversion rate method do not apply to the solution of the pyrolysis activation energy of ryegrass. The pyrolysis activation energy for the two decomposition stages, as calculated by the Kissinger method, is 165.73 and 185.86 kJ/mol-1 in the air atmosphere, and 219.99 and 277.02 kJ/mol-1 in a nitrogen atmosphere, respectively. The activation energy and mechanism function of ryegrass pyrolysis calculated by using the S-S method are as follows: [-ln(1-α)]2, 119.79, 104.31, 95.75, and 91.93 kJ/mol-1 in air atmosphere, (1-α)-1, 176.64, 67.89, 61.15, and 54.25 kJ/mol-1 in nitrogen atmosphere, respectively. The activation energy of ryegrass pyrolysis, as determined by both the Kissinger method and S-S method, was found to be higher under an air atmosphere compared to a nitrogen atmosphere.

Thermal transformations of perfluorooctanoic acid (PFOA): Mechanisms, volatile organofluorine emissions, and implications to thermal regeneration of granular activated carbon.

Thermal treatment is effective for the removal of perfluorooctanoic acid (PFOA). However, how temperatures, heating methods, and granular activated carbon (GAC) influence pyrolysis of PFOA, and emission risks are not fully understood. We studied thermal behaviors of PFOA at various conditions and analyzed gaseous products using real-time detection technologies and gas chromatography-mass spectrometry (GC-MS). The thermal decomposition of PFOA is surface-mediated. On the surface of quartz, PFOA decomposed into perfluoro-1-heptene and perfluoro-2-heptene, while on GAC, it tended to decompose into 1 H-perfluoroheptane (C7HF15). Neutral PFOA started evaporating around 100 â„ƒ without decomposition in ramp heating. During pyrolysis, when PFOA was pre-adsorbed onto GAC, it was mineralized into SiF4 and produced more than 45 volatile organic fluorine (VOF) byproducts, including perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs). The VOF products were longer-chain (hydro)fluorocarbons (C4-C7) at low temperatures (< 500 â„ƒ) and became shorter-chain (C1-C4) at higher temperatures (> 600 â„ƒ). PFOA transformations include decarboxylation, VOF desorption, further organofluorine decomposition and mineralization in ramp heating of PFOA-laden GAC. Decarboxylation initiates at 120 â„ƒ, but other processes require higher temperatures (>200 â„ƒ). These results offer valuable information regarding the thermal regeneration of PFAS-laden GAC and further VOF control with the afterburner or thermal oxidizer.

Machine learning constructs the microstructure and mechanical properties that accelerate the development of CFRP pyrolysis for carbon-fiber recycling.

The increasing use of carbon-fiber-reinforced plastic (CFRP) has led to its post-end-of-life recycling becoming a research focus. Herein, we studied the macroscopic and microscopic characteristics of recycled carbon fiber (rCF) during CFRP pyrolysis by innovatively combining typical experiments with machine learning. We first comprehensively studied the effects of treatment time and temperature on the mechanical properties, graphitization degree, lattice parameters, and surface O content of rCF following pyrolysis and oxidation. The surface resin residue was found to largely affect the degradation of the mechanical properties of the rCF, whereas oxidation treatment effectively removes this residue and is the critical recycling condition that determines its mechanical properties. In contrast, pyrolysis affected graphitization in a more-pronounced manner. More importantly, a random forest machine-learning model (RF model) that optimizes using a particle swarm algorithm was developed based on 336 data points and used to determine the mechanical properties and microstructural parameters of rCF when treated under various pyrolysis and oxidation conditions. The constructed model was effectively used to forecast the recovery conditions for various rCF target requirements, with the predictions for different recycling conditions found to be in good agreement with the experimental data.