Search Results (248)

Identifying suitable catalyst types and efficient loading methods remains a key research challenge for implementing the in situ catalytic pyrolysis of tar-rich coal. This study investigated a lignite and a gas coal, employing NiCl₂ solution for Ni²⁺ catalyst loading via room-temperature impregnation and hydrothermal treatment on coal particles sized 6–13 mm. The efficiency of Ni²⁺ loading through hydrothermal treatment and the characteristics of pyrolysis product distribution and composition before and after treatment were examined. The results indicated that after NiCl₂ solution impregnation, the Ni²⁺ content in lignite increased from nearly undetectable to over 20 mg/g, whereas in gas coal, it only rose to less than 2 mg/g. Ion exchange is hypothesized to be a primary pathway for Ni²⁺ loading into coal. After hydrothermal treatment at 170 °C, the Ni²⁺ loadings in lignite and gas coal reached 33.6 and 1.45 mg/g, respectively. The loaded Ni²⁺ exhibited distinct catalytic effects on the two coals. For lignite, Ni²⁺ catalyzed the deoxygenation of oxygen-containing compounds and the aromatization of aliphatic hydrocarbons. For gas coal, hydrothermal treatment with NiCl₂ solution at 170 and 220 °C promoted hydrogen transfer reactions, resulting in an increase in tar yield from 10.67% to 11.30% and 11.64%, respectively. Also, the H₂ yield decreased, accompanied by a decrease in aromatic hydrocarbons and an increase in phenolic compounds within the tar. Full article

Chlorinated aliphatic hydrocarbons (CAHs) are some of the most widely distributed organic pollutants in underground environments and have high biological toxicity. This research aims to prepare an effective adsorbent comprising biochar and magnetite (MBC) to remove CAH pollution from soil. Optimization of the preparation and adsorption performance of MBC was investigated. The results of the adsorption experiment, combined with scanning electron microscopy (SEM) observations, show that the best raw material and pyrolysis temperature were coconut shell and 500 °C respectively. The Fourier transform infrared (FTIR) and X-ray diffraction (XRD) pattern characterizations, as well as the adsorption results, demonstrated the successful synthesis and enhancement effect of MBC for CAHs. The adsorption of CAHs on Fe₃O₄-loaded biochar was improved by 34.40–222.25% during pyrolysis at 500–900 °C. Additionally, MBC with a 10% Fe₃O₄ content had the best effect on three types of CAHs at low concentrations. A comparative pore analysis of MBC with different doses of Fe₃O₄ was carried out to reveal the relationship between the pore characteristics and adsorption properties. Furthermore, competitive adsorption experiments demonstrated that 4 wt% MBC addition significantly reduced the soil-bound TCE by 48.6%. Overall, these results indicated that MBC was an effective adsorbent for CAH removal from the polluted underground environment. Full article

This study aims to assess the by-products generated through the thermal and catalytic pyrolysis of the organic matter and paper fractions of municipal solid waste (MSW) in different socioeconomic regions, through the yields of reaction products (bio-oil, biochar, H₂O, and gas), acid value and chemical composition of bio-oils, and characterization of biochar, on a laboratory scale. The organic matter and paper segregated from the gravimetric composition of the total waste sample were subjected to drying, crushing, and sieving pre-treatment. The experiments were carried out at 450 °C and 1.0 atmosphere, and at 400 °C and 475 °C and 1.0 atmosphere, using a basic catalyst, Ca(OH)₂, at 10.0% by mass, in discontinuous mode. The bio-oil was characterized by acidity value and the chemical functions present in the bio-oil identified by FT-IR, NMR, and composition by GC-MS. The biochar was characterized by SEM/EDS and XRD. The bio-oil yield increased with the addition of the catalyst and the pyrolysis temperature. For catalytic pyrolysis, bio-char and gas yields increased slightly with the Ca(OH)₂ content, while bio-oil and H₂O phases remained constant. The GC-MS of the liquid reaction products identified the presence of hydrocarbons and oxygenates, as well as nitrogen-containing compounds, including amides and amines. The acidity of the bio-oil decreased with the addition of the basic catalyst in the process. The concentration of hydrocarbons in the bio-oil appeared with the addition of the catalyst in the catalytic pyrolysis process as the catalytic deoxygenation of fatty acid molecules occurred, through decarboxylation/decarbonylation, producing aliphatic and aromatic hydrocarbons, introducing the basic catalyst into the thermal process. Full article

Amaranth is important for the agro-industrial complex. However, when extracting flour and oil from seeds, a lot of waste remains. Waste recycling by co-pyrolysis aims at obtaining new products with high added value. This study examined a combination of A. cruentus (AC) residues and low-density polyethylene (LDPE) waste. The addition of polymer was aimed at obtaining hydrocarbon-rich pyrolysis liquid and biochar. Pyrolysis was performed on an experimental setup, along with thermogravimetry–Fourier infrared spectroscopy–gas chromatography mass spectrometry (TG-FTIR-GC MS), to examine the thermochemical conversion. Experiments were carried out using a thermogravimetric analyzer at heating rates of 5, 10, and 20 °C/min. The average activation energy values for the pyrolysis of the AC/LDPE blend by the Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS) techniques were 301.39 kJ/mol and 287.69 kJ/mol, respectively. A visual examination of the correlations of the kinetic parameters of AC/LDPE was carried out using the Kriging method. The pyrolysis liquid from AC contains 38.14% hydrocarbons, with the main part being aliphatic hydrocarbons. During the pyrolysis of the AC/LDPE mixture, hydrocarbons were found in the resinous and waxy organic fractions of the pyrolysis liquid. The composition and properties of AC and AC/LDPE biochar are similar, and they can both be applied to agriculture. Full article

In this study, non-isothermal pyrolysis of a mixture of disposable surgical face masks (FMs) and nitrile gloves (NGs) was conducted, using a heating rate of 100 °C/min, N₂ flowrate of 100 mL/min, and temperatures between 500 and 800 °C. Condensable product yield peaked at 600 °C (76.9 wt.%), with gas yields rising to 31.0 wt.%, at 800 °C. GC-MS of the condensable product confirmed the presence of aliphatic compounds (>90%), while hydrogen, methane, and ethylene dominated the gas composition. At 600 °C, gasoline (C₄ to C₁₂)-, diesel (C₁₃ to C₂₀)-, motor oil (C₂₁ to C₃₅)-, and heavy hydrocarbon (C₃₅₊)-range compounds accounted for 23.7, 46.7, 12.5, and 17.1%, of the condensable product, respectively. Using model-free methods, the average activation energy and pre-exponential factor were found to be 309.7 ± 2.4 kJ/mol and 2.5 ± 3.4 × 10²⁵ s⁻¹, respectively, while a 2-dimensional diffusion mechanism was determined. Scale-up runs confirmed high yields of condensable product (60–70%), with comparable composition to that obtained from lab-scale tests. The pyrolysis oil exceeds acceptable oxygen, nitrogen, chlorine, and fluorine levels for industrial steam crackers—needing pre-treatment—while other contaminants like sulphur and metals could be managed through mild blending. In summary, this work offers a sustainable approach to address the environmental concerns surrounding disposable FMs and NGs. Full article

Combustion of aviation jet fuel emits a complex mixture of pollutants linked to adverse health outcomes among airport personnel and nearby communities. While epidemiological studies showed the detrimental effects of aviation-derived air pollutants on human health, the molecular mechanisms of the interactions of these pollutants with cellular biomolecules like proteins that drive the adverse health effects remain poorly understood. In this study, we performed molecular docking simulations of 272 pollutant–protein complexes using AutoDock Vina 1.2.7 to characterize the binding strength of the pollutants with the selected proteins. We selected 34 aviation-derived pollutants that constitute three chemical categories of pollutants: volatile organic compounds (VOCs), polyaromatic hydrocarbons (PAHs), and organophosphate esters (OPEs). Each pollutant was docked to eight proteins that play critical roles in endocrine, metabolic, transport, and neurophysiological functions, where functional disruption is implicated in disease. The effect of binding of multiple pollutants was analyzed. Our results indicate that aliphatic and monoaromatic VOCs display low (<6 kcal/mol) binding affinities while PAHs and organophosphate esters exhibit strong (>7 kcal/mol) binding affinities. Furthermore, the binding strength of PAHs exhibits a positive correlation with the increasing number of aromatic rings in the pollutants, ranging from nearly 7 kcal/mol for two aromatic rings to more than 15 kcal/mol for five aromatic rings. Analysis of intermolecular interactions showed that these interactions are predominantly stabilized by hydrophobic, pi-stacking, and hydrogen bonding interactions. Simultaneous docking of multiple pollutants revealed the increased binding strength of the resulting complexes, highlighting the detrimental effect of exposure to pollutant mixtures found in ambient air near airports. We provide a priority list of pollutants that regulatory authorities can use to further develop targeted mitigation strategies to protect the vulnerable personnel and communities near airports. Full article

Fischer–Tropsch synthesis (FTS) facilitates the conversion of syngas, derived from feedstocks such as biomass, coal, and natural gas, into valuable hydrocarbons (HCs). This investigation employed optimization methods, specifically Gibbs energy minimization, to perform a thermodynamic characterization of the low-temperature Fischer–Tropsch (LTFT) reaction for HC generation. The CONOPT3 solver within GAMS 23.2.1 software was utilized for solving the developed model. To represent the complex FTS product spectrum, twenty-three compounds, encompassing C₂–C₂₀ aliphatic hydrocarbons, were considered using a stoichiometric framework. The study explored the impact of operational parameters, including temperature (350–550 K), pressure (5–30 bar), and H₂/CO molar feed ratio (1.0–2.0/0.5–1.0), on hydrocarbon synthesis. Evaluation of the outcomes focused on HC yield and product characteristics. A significant sensitivity of the reaction to operating parameters was observed. Notably, lower temperatures, elevated pressures, and a H₂/CO ratio of 2.0/1.0 were identified as optimal for fostering the formation of longer-chain HCs. The developed model demonstrated robustness and efficiency, with rapid computation times across all simulations. Full article

This paper presents a modern spectroscopic characterization of the synthetic oil from oil sands of Beke, Munaily-Mola, and Dongeleksor. The pyrolysis process was carried out at temperatures up to 580 °C with a controlled heating rate, and the products obtained were analyzed using Fourier transform infrared spectroscopy (FTIR), gas chromatography–mass spectrometry (GC–MSD), and nuclear magnetic resonance (NMR) spectroscopy. The FTIR spectra showed a predominance of aliphatic hydrocarbons in the sample from Munaily-Mola synthetic oil, while the content of aromatic compounds was higher in the sample from Beke. GC–MSD analysis revealed significant differences in the distribution of hydrocarbons between the samples, with the Munaily-Mola sample containing a higher proportion of heavy hydrocarbons. NMR spectroscopy provided additional information about the structural composition of the extracted oil. The results indicate the potential of pyrolysis as an effective method for processing oil sands, while the composition of the product varies depending on the geological origin of the raw materials. These findings provide valuable information for optimizing oil sands processing technologies and improving the efficiency of synthetic oil production. Full article

Rapid economic growth has led to an increase in the use of multilayer plastic packaging, which involves complex polymer compositions and hinders recycling. This study investigated the catalytic pyrolysis of plastic packaging waste in a 3000 cm³ semibatch reactor, aiming to optimize kerosene-like hydrocarbon production. The temperature (420–500 °C), N₂ flow rate (25–125 mL/min), and catalyst loading (5–20 wt.%) were examined individually and in combination with activated carbon and an Fe-doped dolomite (Fe/DM) catalyst. Central composite design (CCD) and response surface methodology (RSM) were used to identify the optimal conditions and synergistic effects. Pyrolysis product analysis involved simulation distillation gas chromatography (Sim-DGC), gas chromatography/mass spectrometry (GC/MS), and Fourier transform infrared (FT-IR) spectroscopy. The optimal conditions (440 °C, 50 mL/min N₂ flow, catalyst loading of 10 wt.% using a 5 wt.% Fe-doped dolomite-activated carbon 0.6:0.4 mass/molar ratio) yielded the highest pyrolysis oil (79.6 ± 0.35 wt.%) and kerosene-like fraction (22.3 ± 0.22 wt.%). The positive synergistic effect of Fe/DM and activated carbon (0.6:0.4) enhanced the catalytic activity, promoting long-chain polymer degradation into mid-range hydrocarbons, with secondary cracking yielding smaller hydrocarbons. The pore structure and acid sites of the catalyst improved the conversion of intermediate hydrocarbons into aliphatic compounds (C₅–C₁₅), increasing kerosene-like hydrocarbon production. Full article

In this study, we investigated the solvent performance of six heavy oils from Xinjiang, China, for coal–oil co-liquefaction (COCL). Autoclave experiments revealed that shale oil vacuum residue (SOVR) provided the best liquefaction performance. The oils were characterized using FT-IR, ¹³C-NMR, ¹H-NMR, and column chromatography, which revealed that they were mainly composed of aliphatic compounds, with minor aromatic and substituted aromatic compounds. The pyrolytic degradation quality indices (PDQIs), solubility parameter (δ_C), and polycyclic aromatic hydrocarbon content (H_A2 + H_A3) were calculated and correlated with liquefaction performance. The results showed a strong linear relationship between H_A2 + H_A3 and oil yield (R² = 0.90), and the aromatic content (AR) was also positively related to oil yield. This study suggests that AR content and H_A2 + H_A3 are effective indicators for evaluating the solvent performance of heavy oils in COCL. Full article

In this study, the chemical compositions of PM_2.5 (particulate matter < 2.5 μm) and the molecular compositions of methanol-soluble organic carbon (MSOC) in suburban Shanghai during summer were measured to investigate the molecular characteristics of organic aerosol (OA) under high humidity. Diurnal variation analysis reveals the influence of relative humidity (RH) on secondary organic aerosol (SOA) components. Organosulfates (OSs), particularly nitrooxy-OSs, exhibit a positive correlation with increasing humidity rather than atmospheric oxidants in this high-humidity site. This suggests that high RH can promote the formation of OSs, possibly through enhancing particle surface area and volume, and creating a favorable environment for aqueous-phase or heterogeneous reactions in the particle phase. A considerable proportion of CHOS compounds may be derived from anthropogenic aliphatic hydrocarbon derivatives. These compounds exhibit slightly elevated daytime concentrations due to increased emissions of long-chain aliphatics from sources such as diesel combustion, as well as photochemically enhanced oxidation to OSs. In contrast, CHONS compounds increased at night, driven by high-humidity liquid-phase oxidation. Terpenoid derivatives accounted for 13.4% of MSOC and contributed over 40% to nighttime CHONS. These findings highlight humidity’s important role in driving daytime and nighttime processing of anthropogenic and biogenic precursors to form SOA, even under low SO₂ and NO_x conditions. Full article

The Hammam–Zriba F–Ba (Zn–Pb) stratabound deposit is located within the Zaghouan Fluorite Province (ZFP), which is the most important mineral sub-province in NE Tunisia, with several CaF₂ deposits occurring mainly along the Zaghouan Fault and corresponding to an F-rich MVT mineral system developed along the unconformity surface between the uppermost Jurassic limestones and the late Cretaceous layers. Petrographic analysis, microthermometry, and Raman spectroscopy applied to fluid inclusions in fluorite revealed various types of inclusions containing brines, oil, CO₂, and CH₄ along with solid phases such as evenkite, graphite, kerogen and bitumen. Microthermometric data indicate homogenization temperatures ranging from 85 °C to 145 ± 5 °C and salinities of 13–22 wt.% NaCl equivalent. This study supports a model of heterogeneous trapping, where saline basinal brines, oil, and gases were simultaneously trapped within fluorite, which indicates fluid immiscibility. The Raman analysis identified previously undetected organic compounds, including the first documented occurrence of evenkite, a mineral hydrocarbon, co-genetically trapped with graphite. The identification of evenkite and graphite in fluid inclusions offers new insights into the composition of hydrocarbon-bearing fluids within the MVT deposits in Tunisia, contributing to an understanding of the mineralogical characteristics of these deposits. The identified hydrocarbons correspond to three oil families. Family I (aliphatic compounds) is attributed to the lower-Eocene Bou-Dabbous Formation, family II (aromatic compounds) is attributed to the Albian Fahdene Formation and the Cenomanian–Turonian Bahloul Formation, and family III is considered as a mixture of aliphatic and aromatic compounds generated by the three sources. The presence of graphite in fluid inclusions could suggest the involvement of a thermal effect from deep-seated sources through the reservoir to the site of fluorite precipitation. These findings suggest that the fluorite mineral system might have been linked with the interaction of multi-reservoir fluids, potentially linked to the neighboring petroleum system in northeastern Tunisia during the Miocene. This study aims to investigate the composition of fluid inclusions in fluorite from the Hammam–Zriba F–Ba (Zn–Pb) deposit, with a particular focus on the plausible sources of hydrocarbons and their implications for the genetic relationship between the mineralizing system and petroleum reservoirs. Full article

The disposal of low-level and intermediate-level radioactive solid waste has aroused widespread concern. In this work, the pyrolysis characterizations of simulated radioactive solid waste, cotton gloves (CG), stain removal cloths (SRC), plastic bags (PB), shoe covers (SC), and ion exchange resins (IER), were analyzed using thermogravimetric analysis, Thermogravimetric–Fourier Transform Infrared Spectrometry–Mass Spectrometry (TG-FTIR-MS) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). The main mass loss stages of CG, SRC, PB, SC, and IER were 240–500 °C, 210–500 °C, 400–550 °C, 180–610 °C, and 25–700 °C, respectively. The average activation energies calculated by three iso-conversional methods were 184.09–211.46 kJ/mol, 172.33–180.85 kJ/mol, 264.63–268.01 kJ/mol, 150.49–184.36 kJ/mol, and 150.72–151.66 kJ/mol, respectively. Pyrolysis of CG and SRC mainly produced CO₂ and oxygenated compounds. SC generated large amounts of HCl during pyrolysis. Combined with rapid pyrolysis analysis, it was shown that CG and SRC mainly produced carbohydrates, aliphatic hydrocarbons, and aromatics. The pyrolysis products of SC mainly consisted of aliphatic hydrocarbons, aromatics, and acids. The pyrolysis products of PB were mainly olefins and alcohols. IER produced large amounts of aromatics during rapid pyrolysis. Specifically, the pyrolysis of IER generated some SO₂. This work provides a theoretical basis and data support for the treatment of mixed combustible radioactive waste. Full article

The surface chemistry of epoxy resin and its composites is critical for their long-term performance across various applications. In this study, we investigate the main reactions occurring on the surface of DEGBA/DEGBF epoxy resin following curing, post-curing, and thermal post-curing processes using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). ToF-SIMS analysis elucidated molecular details, including curing and cross-linking progression, cross-link characteristics, cured resin structure, residual unreacted hardener, cross-linking density, and reaction pathways. Principal Components Regression analysis (PCR) was applied to distinguish between cured and post-cured samples, focusing on specific ions indicative of the curing process. The completion of curing was associated with ions such as C₁₄H₇O⁺, CHO⁺, CH₃O⁺, and C₂₁H₂₄O₄⁺, while unreacted hardener was indicated by C₂₁H₂₄O₄⁺ ions. Cross-linking density and the intensities of aliphatic hydrocarbons were crucial in differentiating curing stages. Calibration ensured that all ion intensities totaled to one, and specific ions were tracked to monitor the states from uncured to post-cured. Negative spectra provided insights into the consumption of hardener molecules during curing and post-curing. The results demonstrated that post-curing enhances the properties of epoxy resin by promoting further cross-linking, reducing residual unreacted groups, and forming a more extensive covalent network. This results in improved mechanical and thermal stability. The molecular changes observed through ToF-SIMS data effectively distinguish between curing and post-curing reactions, contributing to a better understanding and optimization of epoxy resin properties for various applications. Full article

The thermal degradation of wood polymers (cellulose, hemicelluloses, and lignin) results in the production of volatile products, some of which are toxic or act as irritants. In the present work, we focus on the effect of wood treatment on the formation of volatile products, conducting experiments on thermally treated (TTW), flame-retardant-treated (FRW), and untreated (REF) spruce wood. The samples were subjected to thermal loading at 150 °C, 200 °C, and 250 °C with the subsequent collection of degradation products. We evaluated the effect of wood treatment on the formation of volatile organic compounds (VOCs) using gas chromatography–mass spectrometry (GC-MS). The number and quantity of VOCs are significantly affected by the type of wood treatment and the thermal loading temperature. At the temperature of 250 °C, the concentration and number of VOCs increased significantly. The highest number of VOCs was identified in the untreated wood samples (54 compounds, mostly aldehydes, ketones, and phenols), with a lower number being identified in the flame-retardant-treated samples (9 compounds, mainly furfural) and the lowest number being identified in thermally treated wood samples (3 compounds, aliphatic hydrocarbons). Typical volatile products included furfural, furfurylalcohol, and α-pinene. Qualitative and quantitative analysis of VOCs under thermal loading is important in evaluating the wood burning process and the toxic properties of the consequent gaseous products. Full article