The effects of integrating an acid wash with torrefaction pre-treatment on pyrolytic properties of soybean hulls (SH), and subsequent reductions in nitrogen oxides emitted through thermal decomposition are investigated. Soybean hulls were subjected to acid treatment followed by torrefaction treatments over a range of temperature (180°C, 220°C, 260°C, and 290°C) for 30 minutes. Positive correlations were observed between torrefaction temperature and enhancement of SH calorific value, energy density, and fuel ratio. In particular, acid washed torrefied soybean hulls at 260°C treatment was found to be the most effective yielding the highest energy yields (70.31%) EMCEI (energy mass-cohesion efficiency index) (17.35%), and highest thermal resistance. Analysis of kinetic data demonstrated that torrefaction resulted in increasing average activation energy from 193-195 KJ/mol (raw SH) to 223-228 KJ/mol (acid washed torrefied soybean hulls at 290°C) indicating improved thermal resistance due to the pre-treatment process. Thermodynamic data indicated that the enthalpy values ranged from 186-215 KJ/mol (acid washed torrefied soybean hulls-180) to 195-320 KJ/mol (acid washed torrefied soybean hulls at 290°C) and the Gibbs free energy increased from 152.0-152.6 KJ/mol to 156.0-157.0 KJ/mol indicating increased thermodynamic barriers. Analytical data of functional groups indicate that the amount of C-H, C-C, and C=C bonds in SH increased with torrefaction temperatures, whereas, N-H, C-N, C=O, and C-O bond amounts decreased with torrefaction temperatures. Thermal gravimetric mass spectroscopy (TG-MS) data indicated an increase in H2 and CH4 production with a decrease in CO2 and H2O production. Specifically, pyrolysis of acid washed torrefied soybean hulls-260 °C sample produced only a small amount of NO and NOx. This research provides beneficial information related to environmental SH utilization and clean biomass to energy conversion technology development.

Efficient solid-phase systems for rare-earth separation require simultaneous control of adsorption kinetics, capacity, and selectivity under realistic aqueous conditions. Here, dendritic fibrous nanosilica (DFNS) was functionalized with representative organophosphorus extractants to identify an optimal extractant-support combination. Among the screened materials, di-(2-ethylhexyl) phosphoric acid-functionalized DFNS (D-DEHPA) exhibited the highest Dy3+ uptake and was selected for detailed study. D-DEHPA showed rapid adsorption, with apparent equilibrium reached within ∼5 min under the tested conditions, along with a high Langmuir capacity of 153.8 mg/g. Under fully competitive multicomponent conditions, D-DEHPA demonstrated strong selectivity, including preferential uptake of rare-earth ions over competing cations and systematic discrimination across the lanthanide series (SFDy/La = 17.3; SFDy/Tb = 4.3). This selectivity was maintained in complex real matrices, including an industrial rare-earth sludge leachate and dilute natural water, with near-quantitative Dy3+ removal from the natural water, and retained preferential heavy rare-earth uptake in the leachate. Regeneration studies showed retention of useful separation performance over five repeated cycles. These results demonstrate that DFNS-supported deployment of a well-established extractant can deliver rapid uptake and multicomponent selectivity under realistic conditions, providing a promising solid-phase platform for rare-earth recovery while highlighting the importance of support architecture in immobilized-extractant systems.

The catalytic co-pyrolysis of polyethylene terephthalate (PET) and polyolefins (PP/HDPE) presents a promising route for producing benzene, toluene, and xylene (BTX), yet achieving high selectivity remains challenging due to inefficient deoxygenation and limited aromatization. In this study, a Ga-modified HZSM-5 catalyst is reported, which synergistically enhances both acidity and dehydrogenation functions to increase BTX production. A series of Ga/HZSM-5 catalysts with varying Ga loadings (1-23 wt%) were synthesized and systematically characterized. Thermogravimetric analysis revealed a strong synergistic interaction in PET/PP blends, where PP-derived radicals facilitate PET deoxygenation and suppress coking. Under optimized conditions (PET:PP = 1:1, pyrolysis/catalysis temperature = 600oC, residence time = 1.70 s), the 11 wt% Ga/HZSM-5 catalyst achieved a remarkable BTX yield of 76.94 wt%, significantly outperforming unmodified HZSM-5. The introduction of Ga species modulated the acid strength, suppressed over-cracking, and enhanced dehydrogenation activity, thereby promoting the alkylation of benzene with light olefins to form toluene and xylene. Additionally, the catalyst exhibited excellent regenerability and stability over multiple reaction cycles. This work elucidates the dual synergy mechanism, encompassing both feedstock synergy in co-pyrolysis and catalytic synergy over Ga/HZSM-5, thereby offering a strategic framework for designing efficient bifunctional catalysts to valorize mixed plastic wastes.

Bio-based fertilisers (BBFs) derived from waste streams represent a transformative approach to sustainable agriculture, addressing the dual challenges of waste management and food security. This comprehensive review examines recent advances in BBF production technologies, nutrient recovery mechanisms, soil health impacts, and the benefits of a circular economy. This review, based on an analysis of peer-reviewed studies, demonstrates that BBFs consistently improve the physical, chemical, and biological properties of soil while reducing environmental impacts by 15–45% compared to synthetic alternatives. Advanced biological treatment technologies, including anaerobic digestion, vermicomposting, and biochar production, achieve nutrient recovery efficiencies of 60–95% in diverse waste streams. Market analysis reveals a rapidly expanding sector projected to grow from $2.53 billion (2024) to $6.3 billion by 2032, driven by regulatory support and circular economy policies. Critical research gaps remain in standardisation, long-term performance evaluation, and integration with precision agriculture systems. Future developments should focus on AI-driven optimisation, climate-adaptive formulations, and nanobioconjugate technologies.

Understanding the synergistic interactions between biomass and sulfur-containing additives during co-pyrolysis is crucial for controlling sulfur transformation pathways and tailoring sulfur-doped carbonaceous materials. In the present study, the pyrolysis conversion of rice straw, thiourea, and their blend were probed using thermogravimetric analysis coupled with evolved gas analysis (TG-FTIR-MS and TG-GC/MS), isoconversional kinetics, master-plots method, and thermodynamic evaluation. The thiourea addition could alter the decomposition behavior, shifting the decomposition peaks from 335 to 348 degrees C for rice straw and 255-266 degrees C for thiourea to 206-241 degrees C and 331-347 degrees C for the blend, indicating intermolecular interactions during co-pyrolysis. Product evolution analysis revealed a transition from oxygenated volatiles (e.g., acetic acid and furan derivatives) to sulfur-containing species such as methanethiol and carbonyl sulfide, demonstrating modified reaction pathways induced by thiourea. Thermokinetics analysis showed that the average Ea of the blend (200 kJ mol1) exceeded those of individual rice straw (157 kJ mol 1) and thiourea (103 kJ mol 1), reflecting kinetic restructuring and the formation of thermally stabilized intermediates. Master-plots analysis identified a three-dimensional phase-boundary (R3) mechanism as dominant at conversions below 0.65, with deviations at higher conversions due to multi-step reactions. Linear correlations between apparent activation energy and pre-exponential factor indicated the occurrence of kinetic compensation effect, while thermodynamic study revealed the enthalpy-entropy compensation, with compensation temperatures matching experimental conditions. The positive values for enthalpy change (140-201 kJ mol1) and Gibbs free energy change (141-109 kJ mol1) indicating the non-spontaneous nature of these conversions. These results provided integrated kinetic, thermodynamic, and mechanistic insights into sulfur-biomass interactions during co-pyrolysis and offered guidance for controlling sulfur transformation in biomass-derived carbonaceous materials.

Sewage sludge (SS) poses significant environmental and socio-economic challenges due to its high moisture content and limited disposal options. Hydrothermal carbonization (HTC) has been identified as an effective pretreatment method to enhance the stability and reactivity of hydrochar (HC) for energy applications. This study investigates the co-gasification behavior of pyrolyzed HC derived from SS and coal char in CO2 environments, with a focus on the influence of temperature (850 degrees C, 900 degrees C, and 950 degrees C) and particle size (35 mu m, 110 mu m, 250 mu m, and 430 mu m) on gasification reactivity and carbon conversion. Experimental results show that smaller particles (35 mu m) exhibited the highest reactivity due to their larger surface area-to-volume ratio, achieving a gasification rate of 0.010945 s-1 at 950 degrees C. Increasing the temperature significantly enhanced carbon conversion, with conversion rates accelerating particularly at 950 degrees C during the initial phases. Coal char demonstrated rapid thermal degradation, while HC displayed superior thermal stability and reduced reactivity at higher temperatures due to its more condensed carbon structure. Notably, HC concentrations (15 %) improved overall reactivity compared to lower concentrations (5 %), emphasizing the synergistic effects of co-gasification. This study highlights the critical role of temperature and particle size in optimizing waste-to-energy conversion processes, offering actionable insights for enhancing efficiency and sustainability in waste management systems.

The co-gasification of hydrothermally carbonized sewage sludge-derived hydrochar (HC) with SH coal under a CO2 atmosphere presents a promising route for sustainable energy generation and CO2 mitigation. This study systematically investigates the influence of HC-to-coal blending ratios and gasification temperatures on syngas composition, tar formation, and ash content. A blend of 25 wt % HC with 75 wt % coal at 950 degrees C was found to be optimal, achieving a 21.32 % ash and elevating the syngas lower heating value to 8.49 MJ/Nm(3), thereby indicating enhanced gasification efficiency. The optimized blend was further evaluated at 800-950 degrees C to elucidate temperature-dependent behavior. Gas analysis revealed that CO2 remained the dominant component (>60 vol %), while H-2 concentration increased from 40 % to 58 % with rising HC content due to intensified thermal cracking and organic matter depolymerization. Concurrently, CO concentration rose significantly from 16 % at 800 degrees C to 59 % at 950 degrees C, attributed to enhanced Boudouard and water-gas shift reactions facilitated by the CO2 environment. Tar analysis showed an increase in polycyclic aromatic hydrocarbons (PAHs) with higher HC ratios, highlighting a trade-off between syngas quality and tar burden. This work provides a comprehensive mechanistic insight into HC-coal co-gasification, underscoring the critical role of temperature and blending optimization in maximizing syngas yield while minimizing undesirable byproducts. The findings support co-gasification as a viable waste-to-energy pathway for sewage sludge valorization and reduced reliance on fossil fuels.

The increasing presence of tetracycline antibiotics in aquatic ecosystems poses a critical environmental challenge, necessitating innovative remediation strategies. This study presents the development and characterization of starch-functionalized iron-graphene oxide (SFIGO) and starch-functionalized iron oxide (SFIO) nanocomposites adsorbents for tetracycline removal from water, with emphasis on sustainable synthesis and enhanced performance. Biluochun tea and cassava extract were used as renewable precursors in green synthesis to create a composite material that combines iron oxide's magnetic properties, graphene oxide's high surface area, and starch's biocompatibility. Comprehensive characterization using FTIR, XRD, SEM-EDX, TEM, and XPS revealed SFIGO's unique hierarchical architecture, featuring wrinkled graphene oxide sheets with well-dispersed iron-oxide nanoparticles. Batch adsorption studies demonstrated SFIGO's superior performance, achieving a maximum adsorption capacity of 865.79 mg/g at 298 K, significantly higher than SFIO's 634.83 mg/g. The adsorption process followed pseudo-second-order kinetics and showed endothermic behavior, with negative Gibbs free energy values, confirming process spontaneity. Multiple binding mechanisms, including π-π interactions, electrostatic attractions, and surface complexation, contributed to SFIGO's enhanced performance. The material demonstrated robust performance across various water matrices and maintained high removal efficiency. These findings advance our understanding of composite materials in environmental remediation and provide a sustainable solution for pharmaceutical pollutant removal.

This study investigated the multicomponent pyrolysis kinetics and thermodynamics of sea buckthorn branch (SBB) biomass to assess its bioenergy potential. Thermogravimetric analysis coupled with Fraser-Suzuki deconvolution identified three pseudo-components (PS-HC, PS-CL, and PS-LG) with peak temperatures of 283-305 degrees C, 344-366 degrees C, and 400-422 degrees C, respectively. Py-GC/MS analysis showed that C16-C28 alkanes and acid were the dominant products, consistent with the significant C-H and C=O group vibrations in the FTIR analysis. Activation energies for each pseudo-component from four isoconversional methods was comparable, showing an increasing order of PS-HC (157.70 kJ/mol) < PS-CL (182.53 kJ/mol) < PS-LG (228.87 kJ/mol). The master-plots method indicated that the reaction mechanisms followed 3rd, 1st and 4th order models, respectively. Positive values for Delta H (152.59, 177.17, and 224.43 kJ/mol) and Delta G (157.47, 176.99, and 190.47 kJ/mol) indicated higher energy barriers, especially for PS-LG, and lower spontaneity of the conversion process. These results highlighted the energy potential of SBB as a feedstock for bioenergy production and provided valuable insights into reactor design and process optimization for large-scale application.

Waste tire (WT) pyrolysis is a well-known technique for the production of fuel, but the formation of pollutants such as PAHs, S-compounds and N-compounds is inevitable due to the existence of sulfur, nitrogen and several additives. The co-pyrolysis of waste tire with biomass can be a viable solution to inhibit the pollutants to mitigate environmental issues. Therefore, co-pyrolysis of waste tire and corn plant stalk (CPS) is performed in TG-MS and Py-GCMS to investigate the synergistic effect. The addition of CPS improved pyrolysis efficiency of WT which resulted in earlier decomposition temperature and reduction in residual from 35.44 wt% to 27.75 wt%. Kinetics and thermodynamic analysis revealed that the average activation energy of co-pyrolysis blends decreased from 83.9 kJ/mol to 46.3 kJ/mol and the addition of CPS avoid the activation complex. The peaks intensities of SO2 and H2S were highest compared to COS, CS2 and CH3SH in WT100 but NH3 and HNCO in CPS100 showed maximum peaks than HCN, NO. The peaks of 9 series of gaseous PAHs in WT100 were higher than CPS100. The blend ratios WT/CPS 2:2 and WT/CPS 1:3 reduced the emission of gaseous sulfur, nitrogen and PAHs compounds. The effect of final pyrolysis temperature and blend ratios in Py-GCMS analysis unveiled that co-pyrolysis maxing ratio WT/CPS 2:2 at 500 degrees C effectively minimized the phenolic, aldehydes, ketones, and acids which enhanced the fuel quality as well as lowered the benzene derivatives/ single ring aromatic hydrocarbons (SRAH) which are regarded as PAHs precursors. Furthermore, the difference between experimental and calculated yield confirms that the synergistic effect completely inhibited PAHs and decreased the N-compounds and S-compounds as well as increased the alkene and olefins. So, the results indicated that co-pyrolysis of WT with biomass can significantly restrain the pollutants and enhance the pyrolytic oil quality which can be used as an alternative environmental friendly fuel.

The rising levels of atmospheric carbon dioxide (CO2) necessitate urgent and effective strategies for its capture and utilization. Among the various CO2 valorization pathways, the conversion of CO2 into methanol has gained considerable attention due to its dual role in reducing greenhouse gas emissions and serving as a renewable fuel and chemical feedstock. This review uniquely combines bibliometric analysis of 13,289 peer-reviewed publications (2012–2023) with an evaluation of Cu-based catalyst advancements, addressing critical gaps in the literature. A bibliometric analysis highlights the key trends, collaborations, and research gaps in the field. Among the catalytic systems, noble metals, though highly active, are uneconomical for large-scale applications, while non-noble metals, such as nickel, exhibit limited activity due to undesired reaction pathways. In comparison, Cu-based catalysts overcome these challenges by offering a balance of activity, selectivity, and cost-effectiveness. Special emphasis is placed on the CO2 to methanol conversion pathways, with insights into thermodynamic constraints, emerging solutions, and potential directions for future research. By consolidating the current state of knowledge, this review identifies significant opportunities for advancing CO2 conversion technologies, particularly in methanol synthesis, positioning it as a promising strategy for sustainable carbon management and energy production.

Thermal treatment of spent lithium-ion batteries offers the benefits of decomposing organic components while concentrating valuable metals. This work investigated the kinetics, thermodynamics, and evolved products during the protection board pyrolysis under N2 and CO2 atmospheres. The degradation process was divided into stages of below 400 degrees C, 400-700 degrees C, and 700-900 degrees C. Peak temperatures at the maximum mass loss rate were observed at 359-399 degrees C in NQand 367-393 degrees C in COQ. The primary products evolved from phenolics into ketones and acids, and eventually into alkanes. Brominated products such as bromomethane and 1-bromobutane were also detected, indicating the requirement of debromination to improve the usability of pyrolysis products. The average activation energies were determined to be 218.33 kJ/mol in NQand 308.91 kJ/mol in COQ. D4 and D1 reaction mechanisms were found to best describe the pyrolysis process in two atmospheres. Positive values of Delta H and Delta G indicated the endothermic and non-spontaneous characteristics. The difference between Delta H and Ea values ranged from 5.26 to 7.70 kJ/mol in NQand 5.12-7.48 kJ/mol in COQ, indicating a high possibility of overcoming the potential energy barrier.

The accelerated deployment of solar photovoltaic (PV) systems will inevitably lead to an increasing number of end-of-life PV panels. This will raise significant environmental concerns and could limit the expansion of renewable energy systems. In this study, the pyrolysis behavior, kinetics, thermodynamics, and the evolution of products from the typical back sheet Tedlar (R)/Polyester/EVA (TPE) were investigated. Additionally, the kinetic compensation effect (KCE) and enthalpy-entropy compensation (EEC) were investigated. The decomposition of TPE sample was found to occur in three stages: below 300 degrees C, 300-600 degrees C, and 600-900 degrees C, with corresponding mass loss of 0.12-1.55, 79.22-83.94 and 2.07-4.73 wt%. Significant absorption peaks related to C--O and C-O/ C-C groups were observed during this process. A greater release of gaseous products was observed between 400 and 600 degrees C, with benzoic acid and its derivatives as the predominant products. Activation energies from the FWO model showed a decreasing trend from 166.55 to 99.53 kJ mol- 1 over the conversion rate of 0.2-0.9. KCE was observed during TPE degradation and the reconstructed reaction model f (alpha) = alpha- 0.0083(2 alpha- 0.02603)- 1 showed a better fit with the experimental data. Thermodynamic analysis indicated that TPE decomposition was endothermic and non-spontaneous. The comparison between Tcomp (728.22 K) and Texp (793.33 K) values indicated the presence of EEC. The high correlation between Delta Gcom and Delta Gexp values further confirmed the validity of assumed function. The findings from present study are expected to be valuable in advancing the recycling of endof-life PV panels, contributing to the development of a circular economy.

The accelerated deployment of solar photovoltaic (PV) systems will inevitably result in an increasing volume of end-of-life PV panels, which will pose significant environmental challenges and could potentially hinder the growth of renewable energy systems. This study provided a comprehensive examination of the pyrolysis behavior, kinetics, thermodynamics, and evolved products of typical back sheet PVDF/PET/fluorine film (KPF). In addition, an analysis of the enthalpy-entropy compensation (EEC) was performed. Reactive force field molecular dynamics (ReaxFF-MD) simulations were employed to identify atomic-level intermediates and investigate the reaction pathway. The decomposition of KPF sample occurred in three stages, characterized by temperature ranges of below 473.15 K, 473.15-923.15 K, and 923.15-1173.15 K. The corresponding mass losses were found to be 0.61-0.90, 78.30-82.06, and 1.38-2.56 wt%, respectively. The predominant products identified included benzoic acid and its derivatives, which corroborated the strong presence of the C=O group in the FTIR analysis. ReaxFF-MD simulations revealed the formation of C7H4O2, C7H4O and C7H5O2 species, and the decomposition process was found to involve random scission, decarboxylation and decarbonylation reactions. Activation energies from the FWO, KAS, and Friedman methods exhibited a declining trend, decreasing from 72.12 to 40.92 kJ mol-1. The master-plot analysis indicated that the P2 mechanism provided a more accurate description of KPF pyrolysis. The positive Delta H and Delta G values confirmed that KPF decomposition was an endothermic and nonspontaneous process. The Delta H-Delta S relationship indicated the presence of an EEC, with a compensation temperature of 687.49 K and an experimental temperature of 766.60 K.

Environmental co-contamination with antibiotics and heavy metals represents an escalating global threat, with tetracycline (TC) and lead (Pb) exhibiting synergistic toxicity mechanisms that severely compromise soil ecosystem health, plant productivity, and food safety beyond the impacts of individual contaminants. This study investigated the efficacy of green-synthesized iron-graphene oxide nanocomposites (IGO) in remediating agricultural soils co-contaminated with TC and Pb. Co-contamination of antibiotics and heavy metals poses significant threats to soil health, plant growth, and human wellbeing through synergistic interactions. Pot experiments using Lactuca sativa as a model plant were conducted with different concentrations of TC (10 and 100 mg kg(-1)) and Pb (100 mg kg(-1)), with and without IGO treatment (100 mg kg(-1)). Results showed IGO significantly reduced TC uptake by 96.4 % in roots and 97.8 % in shoots, while reducing Pb accumulation by 82 % in roots and 47.5 % in shoots. IGO application enhanced plant physiological parameters, with chlorophyll content increasing by 147-192 % and carotenoids by 179-192 % in co-contaminated soils. Oxidative stress markers decreased significantly, with electrolyte leakage reduced by 41-46 % and MDA content by 40-42 %. Soil enzyme activities increased dramatically, with beta-glucosidase showing 92-236 % enhancement. IGO treatment restored beneficial microbial communities, particularly Bacilli and Firmicutes. These findings demonstrate IGO's effectiveness in immobilizing contaminants, alleviating oxidative stress, and improving soil health, offering a promising strategy for remediating co-contaminated agricultural soils.

To achieve the high-value utilization of agricultural and plastic wastes, the catalytic co-pyrolysis behavior of wheat straw (WS) and polystyrene (PS) was systematically investigated using HZSM-5 zeolite as a catalyst. The results revealed that oxygenates and aliphatic hydrocarbons derived from WS pyrolysis were efficiently converted into aromatics over the HZSM-5 catalyst, increasing the yield of monocyclic aromatic hydrocarbons (MAHs) from 7.8% to 30.3%. A significant synergistic effect was observed at a WS:PS ratio of 60:40, where the yield of BTX (benzene, toluene, and xylene) reached 41.1%, exceeding the levels achieved from the catalytic pyrolysis of either WS or PS alone. This synergy originates from the reconstruction of reaction pathways: the hydrogen-rich environment generated by PS promoted hydrodeoxygenation of biomass, which suppressed CO2 formation (−16%) and enhanced carbon atom utilization; meanwhile, HZSM-5 facilitated dealkylation and alkyl transfer reactions, leading to an increase in benzene production (+12%). Moreover, elevating the catalytic temperature helped to inhibit the formation of polycyclic aromatic hydrocarbons (PAHs) and further increased the MAH yield. These findings provide a valuable reference and experimental basis for the synergistic conversion of waste materials into high-value-added aromatics.

This research illustrates the efficacy of hydrothermal carbonization (HTC) as a pretreatment method to improve the pyrolytic performance of wood-derived lignin-rich lignocellulosic biomass (LB), supported by thorough characterization of its derived products such as syngas, tar, and biochar. A systematic comparison of non-HTC-treated LB and HTC-treated LB through their respective pyrolytic-derived biochar (NLB, HLB) obtained across temperatures (400-1000 degrees C) revealed their basic structural and reactivity variations. HTC resulted in a new carbonyl peak with a 28 % increase in CO concentration in derived biochar, with partial aromatization evidenced by CC bonds at 1509 cm(-)(1) . Spectroscopic analysis confirmed that HTC promoted a defective carbon structure in derived biochar while enhancing its crystallinity and maintaining its integrity even at higher temperatures. XPS analysis demonstrated that at 1000 degrees C, HLB-T-10 retained active oxygen functionalities, while its associated pyrolytic products H-2 and CO boosted from 22.45 % to 40.4 % and 32.3-33.4 %, respectively, with drastically lowered CO2 emissions from 39.95 % to 11.5 %. Regulated deoxygenation routes cause tar composition to shift toward desirable aromatic chemicals. This comprehensive strategy offers a sustainable valorization technique that increases syngas generation efficiency, lowers emissions, and optimizes biorefinery product selection.