Search Results (1,326)

The formation and evolution of haze layers in planetary atmospheres play a critical role in shaping their chemical composition, radiative balance, and optical properties. In the outer solar system, the atmospheres of Titan and the giant planets exhibit a wide range of compositional and seasonal variability, creating environments favorable for the production of complex organic molecules under low-temperature conditions. Among them, Uranus—the smallest of the ice giants—has, since Voyager 2, emerged as a compelling target for future exploration due to unanswered questions regarding the composition and structure of its atmosphere, as well as its ring system and diverse icy moon population (which includes four possible ocean worlds). Titan, as the only moon to harbor a dense atmosphere, presents some of the most complex and unique organics found in the solar system. Central to the production of these organics are chemical processes driven by low-energy photons and electrons (<50 eV), which initiate reaction pathways leading to the formation of organic species and gas phase precursors to high-molecular-weight compounds, including aerosols. These aerosols, in turn, remain susceptible to further processing by low-energy UV radiation as they are transported from the upper atmosphere to the lower stratosphere and troposphere where condensation occurs. In this review, I aim to summarize the current understanding of low-energy (<50 eV) photon- and electron-induced chemistry, drawing on decades of insights from studies of Titan, with the objective of evaluating the relevance and extent of these processes on Uranus in anticipation of future observational and in situ exploration. 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

Using density functional theory (M06-2X-D3/def2-TZVP), we investigated the 1,2-addition reactions of NH₃ with a series of heavy imine analogues, G13=P-Rea (where G13 denotes a Group 13 element; Rea = reactant), featuring a mixed G13–P–Ga backbone. Theoretical analyses revealed that the bonding nature of the G13=P moiety in G13=P-Rea molecules varies with the identity of the Group 13 center. For G13=B, Al, Ga, and In, the bonding is best described as a donor–acceptor (singlet–singlet) interaction, whereas for G13=Tl, it is characterized by an electron-sharing (triplet–triplet) interaction. According to our theoretical studies, all G13=P-Rea species—except the Tl=P analogue—undergo 1,2-addition with NH₃ under favorable energetic conditions. Energy decomposition analysis combined with natural orbitals for chemical valence (EDA–NOCV), along with frontier molecular orbital (FMO) theory, reveals that the primary bonding interaction in these reactions originates from electron donation by the lone pair on the nitrogen atom of NH₃ into the vacant p-π* orbital on the G13 center. In contrast, a secondary, weaker interaction involves electron donation from the phosphorus lone pair of the G13=P-Rea species into the empty σ* orbital of the N–H bond in NH₃. The calculated activation barriers are primarily governed by the deformation energy of ammonia. Specifically, as the atomic weight of the G13 element increases, the atomic radius and G13–P bond length also increase, requiring a greater distortion of the H₂N–H bond to reach the transition state. This leads to a higher geometrical deformation energy of NH₃, thereby increasing the activation barrier for the 1,2-addition reaction involving these Lewis base-stabilized, heavy imine-like G13=P-Rea molecules and ammonia. Full article

A model for the flow and thermal explosion of a micropolar gas is investigated, assuming the equation of state for a real gas. This model describes the dynamics of a gas mixture (fuel and oxidant) undergoing a one-step irreversible chemical reaction. The real gas model is particularly suitable in this context because it more accurately reflects reality under extreme conditions, such as high temperatures and high pressures. Micropolarity introduces local rotational dynamic effects of particles dispersed within the gas mixture. In this paper, we first derive the initial-boundary value system of partial differential equations (PDEs) under the assumption of spherical symmetry and homogeneous boundary conditions. We explain the underlying physical relationships and then construct a corresponding approximate system of ordinary differential equations (ODEs) using the Faedo–Galerkin projection. The existence of solutions for the full PDE model is established by analyzing the limit of the solutions of the ODE system using a priori estimates and compactness theory. Additionally, we propose a numerical scheme for the problem based on the same approximate system. Finally, numerical simulations are performed and discussed in both physical and mathematical contexts. Full article

During atmospheric reentry, a significant number of chemical reactions are produced inside the high-temperature shock wave formed upstream of the spacecraft. Chemical reactions can significantly alter the flowfield structure surrounding the vehicle and affect surface properties, including heat transfer, pressure, and skin friction coefficients. In this scenario, the primary goal of this investigation is to evaluate the Quantum-Kinetic chemistry model for computing rarefied reactive gas flow over simple and complex geometries. The results are compared with well-established reaction models available for the transitional flow regime. The study focuses on two configurations, a sphere and the Orion capsule, analyzed at different altitudes to assess the impact of chemical nonequilibrium across varying flow rarefaction levels. Including chemical reactions led to lower post-shock temperatures, broader shock structures, and significant species dissociation in both geometries. These effects strongly influenced the surface heat flux, pressure, and temperature distributions. Comparison with results from the literature confirmed the validity of the implemented QK model and highlighted the importance of including chemical kinetics when simulating hypersonic flows in the upper atmosphere. Full article

High-alumina fly ash may potentially be a valuable source of Ga with a concentration of Ga at 80 mg/kg. Direct adsorption and enrichment of Ga from sulfuric acid leach liquor of high-alumina fly ash is developed in this study. The H-type chelating resin with two carboxy groups exhibited the best adsorption capacity for Ga. The maximum adsorption capacity for Ga was 55 mg/g resin with an adsorption time of 24 h, an initial Ga concentration of 500 mg/L, an adsorption temperature of 55 °C, and an initial acid concentration of 0.1 mol/L. The adsorption process of Ga was in good fit with the Langmuir isotherm and pseudo-second-order reaction kinetics model. The chemical adsorption rate was controlled by an internal diffusion mechanism. The resin had a high selectivity for Ga³⁺ with a K_d over 3600 compared with Fe²⁺, Al³⁺, K⁺, Ca²⁺, and Mg²⁺. The adsorption mechanism was found to be the ion exchange reaction between Ga and H of carboxy and hydroxyl groups. The concentration of Ga in sulfuric acid leach liquor from high-alumina fly ash achieved enrichment from 200 mg/L to 2 g/L. It is an attractive medium for large-scale Ga extraction from high-alumina fly ash. Full article

The Carboniferous–Permian tight sandstone gas reservoirs in the Shenfu area of the Ordos Basin in China are characterized by the widespread development of multiple formations. However, significant differences exist among the tight sandstones of different formations, and their formation mechanisms and key controlling factors remain unclear, hindering the effective selection and development of favorable tight gas intervals in the study area. Through comprehensive analysis of casting thin section (CTS), scanning electron microscopy (SEM), cathodoluminescence (CL), X-ray diffraction (XRD), particle size and sorting, porosity and permeability data from Upper Paleozoic tight sandstone samples, combined with insights into depositional environments, burial history, and chemical reaction processes, this study clarifies the characteristics of tight sandstone reservoirs, reveals the key controlling factors of reservoir quality, confirms the differential evolutionary mechanisms of tight sandstone of different formations, reconstructs the diagenetic sequence, and constructs an evolution model of reservoir minerals and porosity. The research results indicate depositional processes laid the foundation for the original reservoir properties. Sandstones deposited in tidal flat and deltaic environments exhibit superior initial reservoir qualities. Compaction is a critical factor leading to the decline in reservoir quality across all formations. However, rigid particles such as quartz can partially mitigate the pore reduction caused by compaction. Early diagenetic carbonate cementation reduces reservoir quality by occupying primary pores and hindering the generation of secondary porosity induced by acidic fluids, while later-formed carbonate further densifies the sandstone by filling secondary intragranular pores. Clay mineral cements diminish reservoir porosity and permeability by filling intergranular and intragranular pores. The Shanxi and Taiyuan Formations display relatively poorer reservoir quality due to intense illitization. Overall, the reservoir quality of Benxi Formation is the best, followed by Xiashihezi Formation, with the Taiyuan and Shanxi Formations exhibiting comparatively lower qualities. Full article

The slurry aluminizing process is widely employed to enhance the oxidation and corrosion resistance of nickel-based superalloys used in high-temperature environments such as gas turbines and aerospace engines. This study investigates the effects of the concentration of Al vapors in the reactor chamber and the initial slurry layer thickness on the microstructure, chemical composition, and phase composition of aluminide coatings. Coatings were manufactured on Ni-based superalloy substrates using CrAl powders as an aluminum source and chloride- and fluoride-based activator salts. The effect of the initial thickness of the slurry layer was studied by varying the amount of deposited slurry in terms of mg_slurry/cm²_sample (with constant mg_slurry/cm³_chamber). The microstructure and phase composition of the produced aluminide coatings were evaluated by SEM, EDS, and XRD analysis. Slurry thickness can affect concentration gradients during diffusion, and the best results were obtained with an initial slurry amount of 100 mg_slurry/cm²_sample. The effect of the Al vapor phase in the reaction chamber was then investigated by varying the mg_slurry/cm³_chamber ratio while keeping the slurry layer thickness constant at 100 mg_slurry/cm²_sample. This parameter influences the amount of Al at the substrate surface before the onset of solid-state diffusion, and the best results were obtained for a 6.50 mg_slurry/cm³_chamber ratio with the formation of 80 µm coatings (excluding the interdiffusion zone) with a β-NiAl phase throughout the thickness. To validate process flexibility, the same parameters were successfully applied to produce platinum-modified aluminides with a bi-phasic ζ-PtAl2 and β-(Ni,Pt)Al microstructure. Full article

This work deals with the catalytic steam reforming of raw syngas to increase the efficiency of coupling gasification with downstream processes (such as fuel cells and catalytic chemical syntheses) by producing high-temperature, ready-to-use syngas without cooling it for cleaning and conditioning. Such a combination is considered a key point for the future exploitation of syngas produced by steam gasification of biogenic solid fuel. The design and construction of an integrated gasification and gas conditioning system were proposed approximately 20 years ago; however, they still require further in-depth study for practical applications. A 3D model of the freeboard of a pilot-scale, fluidized bed gasification plant equipped with catalytic ceramic candles was used to investigate the optimal operating conditions for in situ syngas upgrading. The global kinetic parameters for methane and tar reforming reactions were determined experimentally. A fluidized bed gasification reactor (~5 kWth) equipped with a 45 cm long segment of a fully commercial filter candle in its freeboard was used for a series of tests at different temperatures. Using a computational fluid dynamics (CFD) description, the relevant parameters for apparent kinetic equations were obtained in the frame of a first-order reaction model to describe the steam reforming of key tar species. As a further step, a CFD model of the freeboard of a 100 kWth gasification plant, equipped with six catalytic ceramic candles, was developed in ANSYS FLUENT^®. The composition of the syngas input into the gasifier freeboard was obtained from experimental results based on the pilot-scale plant. Simulations showed tar catalytic conversions of 80% for toluene and 41% for naphthalene, still insufficient compared to the threshold limits required for operating solid oxide fuel cells (SOFCs). An overly low freeboard temperature level was identified as the bottleneck for enhancing gas catalytic conversions, so further simulations were performed by injecting an auxiliary stream of O₂/steam (50/50 wt.%) through a series of nozzles at different heights. The best simulation results were obtained when the O₂/steam stream was fed entirely at the bottom of the freeboard, achieving temperatures high enough to achieve a tar content below the safe operating conditions for SOFCs, with minimal loss of hydrogen content or LHV in the fuel gas. Full article

This paper investigates the application of non-calcined metal tartrate as a novel alternative pore former to prepare functional ceramic composites to fabricate solid oxide fuel cells (SOFCs). Compared to carbonaceous pore formers, non-calcined pore formers offer high compatibility with various ceramic composites, providing better control over porosity and pore size distribution, which allows for enhanced gas diffusion, reactant transport and gaseous product release within the fuel cells’ functional layers. In this work, nanocrystalline gadolinium-doped ceria (GDC) and Ni-Gd-Ce-tartrate anode powders were prepared using a single-step co-precipitation synthesis method, based on the carboxylate route, utilising ammonium tartrate as a low-cost, environmentally friendly precipitant. The non-calcined Ni-Gd-Ce-tartrate was used to fabricate dense GDC electrolyte pellets (5–20 μm thick) integrated with a thin film of Ni-GDC anode with controlled porosity at 1300 °C. The dilatometry analysis showed the shrinkage anisotropy factor for the anode substrates prepared using 20 wt. The percentages of Ni-Gd-Ce-tartrate were 30 wt.% and 40 wt.%, with values of 0.98 and 1.01, respectively, showing a significant improvement in microstructural properties and pore size compared to those fabricated using a carbonaceous pore former. The results showed that the non-calcined pore formers can also lower the sintering temperature for GDC to below 1300 °C, saving energy and reducing thermal stresses on the materials. They can also help maintain optimal material properties during sintering, minimising the risk of unwanted chemical reactions or contamination. This flexibility enables the versatile designing and manufacturing of ceramic fuel cells with tailored compositions at a lower cost for large-scale applications. Full article

This work presents a one-dimensional (1D) model for simulating the behavior of an FCC riser reactor processing bio-oil. The FCC riser is modeled as a plug-flow reactor, where the bio-oil feed undergoes vaporization followed by catalytic cracking reactions. The bio-oil droplets are represented using a Lagrangian framework, which accounts for their movement and evaporation within the gas-solid flow field, enabling the assessment of droplet size impact on reactor performance. The cracking reactions are modeled using a four-lumped kinetic scheme, representing the conversion of bio-oil into gasoline, kerosene, gas, and coke. The resulting set of ordinary differential equations is solved using a stiff, second- to third-order solver. The simulation results are validated against experimental data from a full-scale FCC unit, demonstrating good agreement in terms of product yields. The findings indicate that heat exchange by radiation is negligible and that the Buchanan correlation best represents the heat transfer between the droplets and the catalyst particles/gas phase. Another significant observation is that droplet size, across a wide range, does not significantly affect conversion rates due to the bio-oil’s high vaporization heat. The proposed reduced-order model provides valuable insights into optimizing FCC riser reactors for bio-oil processing while avoiding the high computational costs of 3D CFD simulations. The model can be applied across multiple applications, provided the chemical reaction mechanism is known. Compared to full models such as CFD, this approach can reduce computational costs by thousands of computing hours. Full article

Unconventional hydrocarbon reservoirs with low matrix permeability (<0.3 mD), high temperatures, and sour conditions present significant challenges for stimulation and production enhancement. This study examines field trials for a large oil and gas operator in the UAE, focusing on tight carbonate deposits with reservoir temperatures above 93 °C and high sour gas content. A novel multi-stage chemical stimulation workflow was created, beginning with a pre-flush phase that alters rock wettability and reduces interfacial tension at the micro-scale. This was followed by a second phase that increased near-wellbore permeability and ensured proper acid placement. The treatment’s core used a thermally stable, corrosion-resistant retarded acid system designed to slow reaction rates, allow deeper acid penetration, and build prolonged conductive wormholes. Simulations revealed considerable acid penetration of the formation beyond the near-wellbore zone. The post-treatment field data showed a tenfold improvement in injectivity, which corresponded closely to the acid penetration profiles predicted by modeling. Furthermore, oil production demonstrated sustained, high oil production of 515 bpd on average for several months after the treatment, in contrast to the previously unstable and low-rate production. Finally, the findings support a reproducible and technologically advanced stimulation technique for boosting recovery in ultra-tight carbonate reservoirs using the acid retardation effect where traditional stimulation fails. Full article

The research reviews and contrasts two studies based on the gas-phase reaction OH + D₂(v, j). In these studies, Quasi-Classical Trajectory (QCT) calculations and the Gaussian Binning (GB) technique were used on the Wu–Schatz–Lendvay–Fang–Harding (WSLFH) potential energy surface. Large sample sizes allow for precise energy state distribution analysis across translational, vibrational, and rotational components in the products. A key observation is the influence of the vibrational and rotational excitation of D₂ on the total angular momentum (J′) of the HOD* product. This study reveals that increasing the vibrational level, vD₂, significantly shifts P(J′) distributions toward higher values, broadening them due to increased isotropy. In contrast, increasing the rotational level, jD₂, results in a smaller shift but introduces greater anisotropy, leading to a more selective distribution of J′ values. The dual Gaussian Binning selection—Vibrational-GB followed by Rotational-GB—further highlights a preference for either odd or even J′ values, depending on the specific excitation conditions. These findings have implications for the development of chemical lasers, as the excitation and emission properties of HOD* can be leveraged in the laser design. Future research aims to extend this study to a broader range of initial conditions, refining the understanding of reaction dynamics in controlled gas-phase environments. Full article

The initial surface reaction of gallium nitride (GaN) grown by atomic layer deposition (GaN-ALD) was investigated using density functional theory (DFT) calculations. Trimethylgallium (TMG) and ammonia (NH₃) were used as gallium (Ga) and nitrogen (N) precursors, respectively. DFT calculations at the B3LYP/6-311+G(2d,p) and 6-31G(d) levels were performed to compute relative energies and optimize chemical structures, respectively. TMG adsorption on Si₁₅H₁₈–(NH₂)₂ and Si₁₅H₂₀=(NH)₂ clusters was modeled, where –NH₂ and =NH surface species served as adsorption sites. The reaction mechanisms in the adsorption and nitridation steps were investigated. The results showed that TMG can adsorb on both surface adsorption sites. In the initial adsorption stage, TMG adsorbs onto =NH- and –NH₂-terminated Si(100) surfaces with activation energies of 1.11 and 2.00 eV, respectively, indicating that the =NH site is more reactive. During subsequent NH3 adsorption, NH₃ adsorbs onto the residual TMG on the =NH- and –NH₂-terminated surfaces with activation energies of approximately 2.00 ± 0.02 eV. The reaction pathways indicate that NH₃ adsorbs via similar mechanisms on both surfaces, resulting in comparable nitridation kinetics. Furthermore, this study suggests that highly reactive NH₂⁻ species generated in the gas phase from ionized NH₃ may help reduce the process temperature in the GaN-ALD process. Full article