Search Results (165)

The horst and graben system in Western Anatolia lies on the eastern boundary of the Aegean extensional system, one of the most active extensional zones in the world. The Şahinali coal basin is located south of the Büyük Menderes Graben, which is part of this system. This study examines the rare earth elements and yttrium (REY) geochemistry, accumulation conditions, and economic potential of the Şahinali coals. Compared to world coals, the REE concentration in Şahinali coals (208.3 ppm) is quite high, and all REY groups are slightly enriched. Light REY (LREY) is dominant compared to medium REY (MREY) and heavy REY (HREY). The most abundant element in this group is Ce, reaching a concentration of 123.3 ppm. REY distribution patterns indicate H-type enrichment in most samples and, to a lesser extent, M-H-type enrichment. Element ratios (Al₂O₃/TiO₂, TiO₂/Zr, La/Sc, Co/Th) and REY anomalies (Ce, Eu, Gd) indicate that the sedimentary input is predominantly derived from felsic rocks, with limited intermediate to mafic contributions. SEM-EDS findings and correlation analyses indicate that REY are predominantly associated with aluminosilicate minerals. LREY-Th and MREY/HREY-Y relationships are supported by monazite and Y-rich illitic K-aluminosilicates. Paleoenvironmental indicators (V/Cr, Ni/Co, U/Th, Sr/Cu, Rb/Sr, Sr/Ba) indicate that the coal accumulated under oxic–suboxic, warm and humid conditions. The average REY oxide (REO) content slightly exceeds the commonly cited 1000 ppm screening threshold for coal ash. The majority of samples contain elevated proportions of critical REY (30.7%–54.3%) and show promising outlook coefficients (C_outl: 0.8–1.7). Together, these results indicate a favourable compositional signature for preliminary REY resource screening in the Şahinali coals, particularly with respect to elements relevant for high-technology applications. Full article

Little is known of a large black shale belt within the Naij Tal Group in the East Kunlun region, which hosts polymetallic deposits, including manganese, vanadium, and cobalt. The recently discovered Dagangou vanadium mineralization is the first black rock series-type vanadium deposit in the East Kunlun region and Qinghai Province and represents a significant find owing to its intermediate scale. This study investigated the mineralogy, major and trace elements, rare earth elements, and platinum group element geochemistry of the Dagangou vanadium deposit. Scanning electron microscopy and energy-dispersive X-ray spectroscopy revealed that the main vanadium-bearing minerals are micas, followed by limonite, clay minerals, feldspar, and jarosite. The SiO₂/Al₂O₃, Co/Zn, Sr/Ba, and Pd/Ir ratios, as well as the Ir content of the ores, indicated strong involvement of hydrothermal activity in the mineralization process. The V/Cr, Ni/Co, and U/Th ratios, as well as the δU values and significant negative δCe anomalies, suggested that the vanadium-bearing black rock series formed in a strongly anoxic reducing environment. The Al₂O₃/(Al₂O₃ + Fe₂O₃) and MnO/TiO₂ ratios, along with weak positive δEu anomalies and strong enrichment of heavy rare earth elements, indicated that mineralization occurred in an extensional tectonic setting. The black shale-hosted vanadium polymetallic deposit formed in a setting that transitioned from an open oceanic deep-sea environment to a progressively shallower continental margin. Full article

The conventional treatment of high-concentration volatile organic compounds (VOCs) relies on energy-intensive dilution to avoid explosion risks. This study proposes an efficient catalytic combustion process treating VOCs directly within the explosive range while recovering reaction heat using Pt/γ-Al₂O₃-based catalysts promoted with La and Ce. Catalysts (0.05–0.5 wt% Pt) were synthesized via impregnation and characterized using FE-SEM, BET, and XRD. Catalytic combustion experiments at VOC concentrations up to 13,000 ppm showed combustion initiation below 200 °C, achieving 83–99% conversions at 300 °C with complete oxidation to CO₂. Although 5 vol.% moisture significantly inhibited low-temperature activity through competitive adsorption, La and Ce promoters (10 wt%) effectively overcame this limitation by increasing surface area (up to 194.93 m²/g) and oxygen mobility. The Ce-promoted catalyst demonstrated superior water tolerance, achieving complete conversion at 200–210 °C due to its high Oxygen Storage Capacity (OSC). Bench-scale validation using a 1 Nm³/h system confirmed industrial feasibility. Operating at 220 °C with 13,000 ppm toluene for 100 h, the catalyst maintained >99.98% conversion with negligible deactivation and THC emissions below 2 ppm. The double-jacket heat exchanger effectively managed reaction heat (limiting temperature rise to ~20 °C) and recovered it as steam. Compared to Regenerative Thermal Oxidation, this Regenerative Catalytic Oxidation approach reduced emissions and energy consumption. This work demonstrates a robust “combustion-with-recovery” strategy for high-concentration VOC treatment, offering a sustainable alternative with high efficiency, stability, and safe energy-integrated operation. Full article

The biogas dry reforming reaction offers a promising route for syngas production while simultaneously mitigating greenhouse gas emissions. Membrane reactors have proven to be an excellent option for hydrogen production and separation in a single unit, where conversion and yield can be enhanced over conventional processes. In this study, a Pd/YSZ membrane integrated with a Ru/CeO₂ catalyst was evaluated for biogas reaction under varying operating conditions. The selective removal of hydrogen through the palladium membrane improved reactant conversion and suppressed side reactions such as methanation and the reverse water–gas shift. Experiments were performed at temperatures ranging from 500 to 600 °C, pressures of 1–6 bar, and a gas hourly space velocity (GHSV) of 800 h⁻¹. Maximum conversions of CH₄ (43%) and CO₂ (46.7%) were achieved at 600 °C and 2 bar, while the maximum hydrogen recovery of 78% was reached at 6 bar. The membrane reactor outperformed a conventional reactor, offering up to 10% higher CH₄ conversion and improved hydrogen production and yield. Also, a comparative analysis between Ru/CeO₂ and Ni/Al₂O₃ catalysts revealed that while the Ni-based catalyst provided higher CH₄ conversion, it also promoted methane decomposition reaction and coke formation. In contrast, the Ru/CeO₂ catalyst exhibited excellent resistance to coke formation, attributable to ceria’s redox properties and oxygen storage capacity. The combined system of Ru/CeO₂ catalyst and Pd/YSZ membrane offers an effective and sustainable approach for hydrogen-rich syngas production from biogas, with improved performance and long-term stability. Full article

A series of novel Ce-modified MnCoAl layered double oxides (Ce/MCA LDOs) were prepared using solvothermal and impregnation methods for NH₃-SCR denitration. Various characterizations, such as X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H₂ temperature-programmed reduction (H₂-TPR) were used to investigate their structural properties and the mechanism of ammonia selective catalytic reduction (NH₃-SCR). The incorporation of Ce was found to effectively integrate into the LDO framework and enhance the catalytic activity over a wide temperature window. Moreover, the thermal stability and resistance of H₂O and SO₂ were evaluated. In situ DRIFTS studies revealed that the reaction follows both the “Langmuir–Hinshelwood” (L–H) and “Eley–Rideal” (E–R) mechanisms. This work provides systematic insights into the design of LDO-based catalysts, demonstrating their potential for practical application in denitration. Full article

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

Studies were conducted on the hydrogen-free processing of model alkanes, straight-run gasoline, and catalytic cracking gasoline using a new synthesized Co-Mo-Ce/ZSM + Al₂O₃ nanocatalyst, which demonstrated high activity in desulfurization. Thus, the mass fraction of sulfur in the resulting gasoline was reduced by almost three times compared to the initial value of 0.0776% to 0.0354% as a result of hydrogen-free processing of straight-run gasoline. The amount of sulfur in the resulting product was reduced by almost an order of magnitude with hydrogen-free processing of catalytic cracked gasoline: from 0.1650 in the original gasoline to 0.0123%. The octane number of the refined straight-run gasoline was 77.9–80.9 according to the research method (RM) and 61.13–65.8 with the motor method (MM). Physical and chemical methods of analysis (BET, TPD-NH₃, TEM, SEM, and XRD) revealed that nano-structured acid sites coexist with nano-dispersed metallic sites on the surface of the Co-Mo-Ce/ZSM + Al₂O₃ catalyst. The functioning of these two types of nano-active sites (metallic and acidic) ensures the polyfunctionality of the catalytic action of the nanoparticles. The following reactions occur simultaneously in the hydrogen-free processing: isomerization, dehydrogenation, dehydrocyclization. Hydrogen-free processing of low-octane gasoline fractions on nanosized zeolite-containing catalysts is one of the most promising methods to obtain high-octane motor gasoline. Full article

The industrial application of CO₂ methanation in Power-to-X (P2X) systems requires the development of highly active catalysts capable of operating at milder temperatures to ensure energy efficiency, while exhibiting high activity, stability and selectivity. This study reports the synthesis and optimization of Ni-based catalysts on Al₂O₃ supports, guided by a Design of Experiments (DoE, 2⁴ factorial design) approach. Initial optimization afforded a robust catalyst achieving 80% CO₂ conversion and >99% CH₄ selectivity at 325 °C. Remarkably, the incorporation of CeO₂ traces to the Ni-based catalyst substantially boosted catalytic activity, enabling higher conversions at temperatures up to 75 °C lower than the unpromoted catalyst. This improvement is attributed to Ni–CeO_x synergy, which facilitates CO₂ activation and Ni reducibility. Both formulations exhibited exceptional long-term stability over 100 h. Furthermore, process intensification via the Sorption-Enhanced Reaction Process (SERP) with the Ni-based catalyst demonstrated even superior efficiency, rapidly increasing CO₂ conversion beyond 95% with the same selectivity range. Our findings establish a clear and consistent pathway for industrial CO₂ valorization through next-generation P2X technology for high-purity synthetic natural gas (SNG) production. This process offers an efficient and sustainable route toward industrial defossilization by converting captured CO₂ and green H₂ into SNG that is readily usable within the existing energy infrastructure. Full article

Thermal barrier coatings (TBCs) are critical for protecting hot-section components in gas turbines and aero-engines. Traditional yttria-stabilized zirconia (YSZ) coatings are prone to phase transformation and sintering-induced failure at elevated temperatures. This study fabricated CeScYSZ (4 mol% CeO₂ and 6 mol% Sc₂O₃ co-doped YSZ)/NiCrAlY TBCs using atmospheric plasma spraying (APS). A five-factor, four-level orthogonal experimental design was employed to optimize spraying parameters, investigating the influence of powder feed rate, spray distance, current, hydrogen flow rate and primary gas flow rate on the coating’s microstructure and mechanical properties. The resistance to calcium–magnesium–alumino–silicate (CMAS) corrosion was compared between CeScYSZ and YSZ coatings. The results indicate that the optimal parameters are a spray distance of 100 mm, current of 500 A, argon flow rate of 30 L/min, hydrogen flow rate of 6 L/min, and powder feed rate of 45 g/min. Coatings produced under these conditions exhibited moderate porosity and excellent bonding strength. After exposure to CMAS corrosion at 1300 °C for 2 h, the CeScYSZ coating demonstrated significantly superior corrosion resistance compared to YSZ. This enhancement is attributed to the formation of a CaZrO₃ physical barrier and the synergistic effect of Ce and Sc in suppressing deleterious phase transformations. This study provides an experimental basis for the preparation and application of high-performance TBCs. Full article

CaO-Al₂O₃-Ce₂O₃ is a potential new-type basic metallurgical slag system for rare earth steel. To investigate the effects of CaF₂ on the melting point and equilibrium phase types of this slag system, the phase equilibrium relationships and extent of the liquid phase region of CaO-Al₂O₃-Ce₂O₃-CaF₂ slag system at 1300 °C, 1400 °C, and 1500 °C in C/CO were determined by the high-temperature phase equilibrium experiment, Scanning Electron Microscope-Energy Dispersive X-ray Spectrometer (SEM-EDX) and X-ray Diffraction (XRD), and the isothermal phase diagram was plotted. The experimental results show that within the composition range in this study, the slag system has five, seven, and six liquid–solid equilibrium coexistence regions at 1300 °C, 1400 °C, and 1500 °C. The involved multiphase equilibrium regions include five two-phase regions (i.e., Liquid + CaO, Liquid + CaO·2Al₂O₃, Liquid + 2CaO·Al₂O₃·Ce₂O₃, Liquid + 2CaO·3Al₂O₃·Ce₂O₃, Liquid + 11CaO·7Al₂O₃·CaF₂), 4 three-phase regions (i.e., Liquid + CaO + 2CaO·Al₂O₃·Ce₂O₃, Liquid + 11CaO·7Al₂O₃·CaF₂ + 2CaO·Al₂O₃·Ce₂O₃, Liquid + CaO·2Al₂O₃ + 2CaO·3Al₂O₃·Ce₂O₃, Liquid + 11CaO·7Al₂O₃·CaF₂ + 2CaO·3Al₂O₃·Ce₂O₃), and 1 four-phase region (i.e., Liquid + CaO + 11CaO·7Al₂O₃·CaF₂ + 2CaO·Al₂O₃·Ce₂O₃). Meanwhile, based on liquid phase compositions under liquid–solid multiphase equilibrium, the slag system’s liquid phase ranges at the experimental temperatures were determined as follows: at 1300 °C: w(CaO)/w(Al₂O₃) = 0.42~0.92, w(Ce₂O₃) = 1.63%~8.02%, w(CaF₂) = 9.17%~21.46%; 1400 °C: 0.28~1.18, 0.9%~12.62%, 1.04%~23.34%, respectively; 1500 °C: 0.23~1.21, 0~14.42%, 0~26.32%, respectively. Full article

The presence of impurities such as Ca, Mg, and Al during the precipitation of rare earths (REs) using ammonium bicarbonate directly affects product purity. It is necessary to optimize precipitation methods and conditions to improve the separation efficiency between REs and impurities. In this study, RE (La and Ce) ions were precipitated using ammonium bicarbonate solution, and the separation efficiency of REs from Al, Fe, Ca, and Mg ions was investigated with or without the addition of triammonium citrate (TAC). The results showed that as long as the precipitation yield of REs was controlled below 94%, Ca and Mg ions would not enter the precipitation in the absence of other impurities, and the purity of the obtained rare earth oxides (RE₂O₃) was close to 100%. The presence of Al and Fe impurities would reduce the separation efficiency of REs from Ca and Mg. Therefore, Al and Fe must be separated before the precipitation of REs. First, Fe was completely precipitated by controlling the pH value to 4.12. Then, by filtering out the isolation and adjusting the pH value to 4.6, approximately 84% of Al³⁺ was precipitated, with a loss of REs of about 6%. Finally, the pH value was increased to 6.43, and REs were completely precipitated, yielding rare earth carbonate. The RE₂O₃ purity of its calcination product was 97.8% with Al and Mg contents of 1.05% and 0.21%, respectively, and no Ca or Fe was detected. This indicated that Mg can enter the product by co-precipitation with Al. To address this, a small amount of TAC was added during the pre-removal of Fe and Al to facilitate the complete removal of Al. By controlling the precipitation yield of REs at 94%, the purity of the final RE₂O₃ reached 99.6% with an Al content of 0.09%. Furthermore, using a continuous precipitation crystallization method, RE₂O₃ purity can be achieved at 99.8% with an Al content of 0.06%. Full article

Nitrogen oxides (NO_x) emissions pose environmental and health risks. Selective catalytic reduction (SCR) is effective for NO_x removal, and using CO as a reductant can eliminate both NO_x and CO. This study explores CuCe catalysts on SiO₂, Al₂O₃, and TiO₂ for CO-SCR. Results show catalytic activity relates to the synergy between lattice oxygen and CuCe species. TiO₂ enhances this interaction, promoting Cu⁺ and lattice oxygen for NO adsorption and dissociation. The CuCe/TiO₂ catalyst achieves 100% NO conversion at 300 °C and 40.2% at 100 °C, indicating excellent low-temperature performance. These findings are valuable for developing efficient SCR catalysts. Full article

The Dongping manganese (Mn) deposit, located within the Lower Triassic Shipao Formation of the Youjiang Basin, is one of South China’s most significant sedimentary Mn carbonate ore deposits. To resolve longstanding debates over its metallogenic pathway, we conducted integrated sedimentological, mineralogical, and geochemical analyses on three drill cores (ZK5101, ZK0301, and ZK1205) spanning the Mn ore body. X-ray diffraction and backscatter electron imaging reveal that the ores are dominated by kutnohorite, with subordinate quartz, calcite, dolomite, and minor sulfides. The low enrichment of U/Al, V/Al, and Mo/Al, as well as positive Ce anomalies, consistently suggest that Mn, in the form of oxides, was deposited in an oxic water column. Carbon isotope compositions of Mn carbonate ores (δ¹³C_VPDB: −2.3 to −6.1‰) and their negative correlation with MnO suggest that Mn carbonate, predominantly kutnohorite, show a diagenetic reduction in pre-existing Mn oxides via organic-matter oxidation in anoxic sediments pore waters. Elemental discrimination diagramms (Mn-Fe-(Co+Ni+Cu) × 10 and Co/Zn vs. Co+Cu+Ni) uniformly point to a hydrothermal Mn source. We therefore propose that hydrothermal fluids supplied dissolved Mn²⁺ to an oxic slope-basin setting, precipitating initially as Mn oxides, which were subsequently transformed to Mn carbonates during early diagenesis. This model reconciles both the hydrothermal and sedimentary-diagenetic processes of the Dongping Mn deposit. Full article

Petrological knowledge on weathering processes controlling the mobility of chemical elements is still limited in the dry tropical zone of Cameroon. This study aims to investigate the mobility of major and trace elements during rhyolite weathering and soil formation in Mobono by understanding the mineralogical and elemental vertical variation. The studied soil was classified as Cambisols containing mainly quartz, K-feldspar, plagioclase, smectite, kaolinite, illite, calcite, lepidocrocite, goethite, sepiolite, and interstratified clay minerals. pH values ranging between 6.11 and 8.77 indicated that hydrolysis, superimposed on oxidation and carbonation, is the main process responsible for the formation of secondary minerals, leading to the formation of iron oxides and calcite. The bedrock was mainly constituted of SiO₂, Al₂O₃, Na₂O, Fe₂O₃, Ba, Zr, Sr, Y, Ga, and Rb. Ce and Eu anomalies, and chondrite-normalized La/Yb ratios were 0.98, 0.67, and 2.86, respectively. SiO₂, Al₂O₃, Fe₂O₃, Na₂O, and K₂O were major elements in soil horizons. Trace elements revealed high levels of Ba (385 to 1320 mg kg⁻¹), Zr (158 to 429 mg kg⁻¹), Zn (61 to 151 mg kg⁻¹), Sr (62 to 243 mg kg⁻¹), Y (55 to 81 mg kg⁻¹), Rb (1102 to 58 mg kg⁻¹), and Ga (17.70 to 35 mg kg⁻¹). LREEs were more abundant than HREEs, with LREE/HREE ratio ranging between 2.60 and 6.24. Ce and Eu anomalies ranged from 1.08 to 1.21 and 0.58 to 1.24 respectively. The rhyolite-normalized La/Yb ratios varied between 0.56 and 0.96. Mass balance revealed the depletion of Si, Ca, Na, Mn, Sr, Ta, W, U, La, Ce, Pr, Nd, Sm, Gd and Lu, and the accumulation of Al, Fe, K, Mg, P, Sc, V, Co, Ni, Cu, Zn, Ga, Ge, Rb, Y, Zr, Nb, Cs, Ba, Hf, Pb, Th, Eu, Tb, Dy, Ho, Er, Tm and Yb during weathering along the soil profile. Full article

The Qieliekeqi siderite deposit, located in the Tashkurgan block of western Kunlun, is a carbonate-hosted iron deposit with hydrothermal sedimentary features. This study integrates whole-rock geochemistry, stable isotopes, and zircon U–Pb–Hf data to investigate its metallogenic evolution. Coarse-grained siderite samples, formed in deeper water, exhibit average Al₂O₃/TiO₂ ratios of 29.14, δEu of 2.69, and δCe of 0.83, indicating hydrothermal fluid dominance with limited seawater mixing. Banded samples from shallower settings show an average Al₂O₃/TiO₂ of 17.07, δEu of 3.18, and δCe of 0.94, suggesting stronger seawater interaction under oxidizing conditions. Both types are enriched in Mn, Co, and Ba, with low Ti and Al contents. Stable isotope results (δ¹³C_PDB = −6.0‰ to −4.6‰; δ¹⁸O_SMOW = 16.0‰ to 16.9‰) point to seawater-dominated fluids with minor magmatic and meteoric contributions, formed under open-system conditions at avg. temperatures of 53 to 58 °C. Zircon U–Pb dating yields an age of 211.01 ± 0.82 Ma, with an average εHf(t) of −3.94, indicating derivation from the partially melted ancient crust. These results support a two-stage model involving Late Cambrian hydrothermal sedimentation and Late Triassic magmatic overprinting. Full article