Soil heavy metal contamination in mining areas poses a serious environmental challenge, requiring monitoring approaches with both wide coverage and high accuracy. Hyperspectral remote sensing provides an effective solution, yet its performance in complex mining environments is often limited by mixed-pixel effects and nonlinear spectral responses. To address these issues, this study proposes a Physically-Constrained Collaborative Endmember Extraction (PCCEE) framework that integrates spectral unmixing with machine learning for multi-element inversion. Using Gaofen-5 hyperspectral imagery, a collaborative workflow combining Pixel Purity Index (PPI), Vertex Component Analysis (VCA), and prior-spectral-constrained Spectral Angle Mapper (SAM) was developed to improve endmember purity and physical interpretability. Among three unmixing models (LMM, NMF, and SVR), the Linear Mixing Model achieved the best balance between accuracy and efficiency. Random Forest regression using retrieved abundances enabled high-accuracy inversion of eight heavy metals (mean R2 = 0.85). Spatial analysis revealed significant co-enrichment of Pb, Cd, and Zn related to sulfide weathering, while PCA distinguished compound and independent pollution sources. The proposed PCCEE framework effectively mitigates mixed-pixel interference and provides a transferable approach for heavy metal monitoring and risk assessment in complex mining environments.
Accelerating hydrogen desorption in large-scale metal hydride reactors requires intensive thermal energy, the thermodynamic efficiency of such high-speed operations is often overlooked. This study establishes a multilevel framework linking transient thermal-fluid dynamics with second-law efficiency to analyze a hybrid heat exchanger reactor. A validated three-dimensional multi-physics model simulates the system behavior under various active heating conditions. The results indicate that aggressive external heating strategies, including high fluid velocities or elevated inlet temperatures, effectively suppress low-temperature zones and shorten reaction times. However, this kinetic improvement incurs a severe thermodynamic penalty. Raising the heat transfer fluid temperature causes the exergy efficiency to drop from roughly 19.7% to below 5.6% due to increased irreversibility losses. Conversely, increasing the initial bed temperature or enhancing the material thermal conductivity proves to be a superior approach. These methods simultaneously boost reaction rates and improve overall exergy efficiency by minimizing the entropy generation associated with large temperature gradients. The findings suggest that relying solely on high-grade external heating is thermodynamically wasteful. Instead, optimizing the initial thermal state and material properties offers a more sustainable pathway for integrating solid-state hydrogen storage into practical energy systems.
Urban agglomerations are crucial for achieving the United Nations Sustainable Development Goals (SDGs). However, uncertainties remain in the indicators and methodologies used to measure their sustainability. This paper establishes and analyzes the SDGs network at national and urban agglomeration levels, highlighting that urban agglomerations are key scale to achieving sustainable development but are far more complex than a single city scale. Then, this paper proposes an assessment framework for urban agglomeration, which includes indicators, methodological approaches, and validation processes. By introducing the multi-level coupling coordination degree, various influencing mechanisms are integrated into the evaluation stage. In addition, this paper constructs redundancy and sensitivity analyses and establishes a correlation network between indicators and SDGs to collectively validate the robustness and international compatibility of the indicator system. This study provides strong support for understanding and promoting the sustainable development of urban agglomerations, contributing to the achievement of the 2030 Agenda.
Traditionally, the commercial Ni(Co)Mo(W)/Al2O3 hydrodesulfurization (HDS) catalysts were prepared with corresponding oxidation precursors and then sulfured with CS2 or H2S, which is complex and time-consuming. Herein, a novel "O-S exchanging" strategy was proposed to directly synthesize a series of highly efficient NiMoS2/Al2O3 HDS catalysts with various Mo loading using MoS42- solution as a novel active precursor, and their catalytic performances were evaluated for 4,6-dimethyldibenzothiophene (4,6-DMDBT) HDS. The experimental results showed that under the same reaction conditions, the catalyst with 15 wt% MoO3 (S-CAT-15) exhibited a HDS rate up to 99.8 % for 240 h, which was not only nearly two times higher than that of O-CAT-15 counterpart prepared by the conventional oxidation precursor with the same metal loading, but also even 1.6 times higher than that of O-CAT-20 with a higher metal loading, demonstrating its excellent HDS performance and outstanding stability. The deep characterization analyses unveiled that the superior HDS performance of S-CAT- 15 was attributed to this novel strategy, which not only notably improved the sulfidation of Mo species, but also considerably promoted the decoration of Ni atoms onto the edges of MoS2 slabs forming more reactive Type-II NiMo-S sites, thereby remarkably enhancing the HDS performances of S-CAT catalysts. This work may offer a novel protocol to guide the fabrication of more efficient industrial hydrogenation catalysts in the future.
Autocatalysis from the by-product metal sulfides plays a critical role in the residual oil hydrotreating (RHT) process. However, it has not been considered to build the catalyst deactivation models, which probably is one important reason that the widely used S-type deactivation models are inaccurate in predicting some RHT processes' deactivation profiles. A three-stage catalyst deactivation model was first developed to fill this gap based on the mechanism inferred from the experimental and literature data. This model accounts for active site formation from by-product metal sulfides, deactivation due to active site coverage by coke formation and metal deposition, active site poisoning by highly-adsorbed species, active phase sintering, and diffusion resistance from the pore blockage at the same time, resulting in a function of dimensionless metals-on-catalyst. Then, the effectiveness of the proposed model was evaluated using the industrial data of an RHT unit and the experimental data from the literature, either in combination with reaction kinetics or independently. Results showed that RHT processes with clear autocatalytic effects may display different types of deactivation profiles from the traditional "S" shape. However, the proposed model was able to accurately track the entire deactivation curve of the RHT process and well predict the product properties. This approach yields valuable insights into the intricate autocatalytic effect that remarkably contributes to the performance modification of RHT catalysts. It is highly recommended that further research should be conducted on this topic, as it shows great potential to significantly advance catalyst and process development.
The hydrotreating of residual oil is crucial for producing cleaner fuels, as catalyst deactivation due to metal deposits, particularly nickel (Ni) and vanadium (V), remains a significant challenge. Contrary to the conventional view that metal deposits invariably poison catalysts, our recent studies have observed an unexpected enhancement in the activity of commercial NiMo/Al2O3 catalysts during industrial operation. This study systematically investigates the mechanism behind this counter-intuitive phenomenon, with a particular focus on the effects induced by nickel. X-ray photoelectron spectroscopy (XPS) analysis revealed that low-concentration of Ni deposits preferentially formed highly active NiMoS phases during the reaction process, thereby minimized the formation of NiSx, a typical poisoning species. This increases the number of reactive sulfur sites, boosting the hydrodesulfurization (HDS) activity for 4,6-dimethyldibenzothiophene (4,6-DMDBT), with the conversion rate rising from 17.1 to 73.3
Introduction: China's pharmaceutical industry, which is historically centered around generic medicines, has largely transformed from imitation to innovation over the past three decades. Despite unprecedented progress, critical challenges remain such as insufficient indigenous research funding, underdeveloped academia-industry relationships, and significant barriers to market access. Areas covered: This perspective examines the evolving pharmaceutical landscape of China, focusing on its participation in global clinical trials and the resultant new drug approvals. Data for this analysis was sourced from several databases (e.g. PharmCube, NextPharma, and PharmaGO), academic reports, and published literature, covering data up to 2024 (unless otherwise specified). This perspective highlights ongoing regulatory challenges, such as inconsistencies in product standards, and the approval processes relative to the U.S.A. and the European Union. There is also an urgent demand for sustained international investment and recognition, partially due to the recent changes in the geopolitical environment. This perspective also discusses China's efforts to implement accelerated approval pathways and foster multilateral development collaborations. Expert opinion: China must align its regulatory policies more closely to the international norm to generate robust trial data that will be readily acceptable to the FDA and EMA. Continued investment in biologics as well as cell and gene therapy and artificial intelligence will drive innovation and enhance competitiveness. Additionally, strengthening the academia-industry collaboration is crucial to obtaining new leads through translational research. Ultimately, structural reforms are required to solidify the country's goal of becoming a major player in the global pharmaceutical market.
A comprehensive insight into the evolution and molecular structure of basic and neutral nitrogen compounds during the residue hydrotreating(RHT) process was gained through ESI(+)/ESI(-) FT-ICR MS analysis of the feedstock and its hydrogenated samples, with hydrodenitrogenation(HDN) ratios of 15.9%-70.1%. This study revealed that carbazoles, characterized by a double bond equivalent(DBE) of 9-11,were the refractory neutral nitrogen compounds during the RHT process. Their recalcitrant nature was primarily due to their low aromaticity and high steric hindrance. Conversely, quinolines(DBEs 7 to 9)were the most abundant basic nitrogen compounds. Through a meticulous analysis of DBE evolution, we revealed the intricate reaction mechanisms of benzocarbazoles and dibenzocarbazoles in residual oil,highlighting the crucial role of quinolines as key intermediates in eliminating these compounds. Interestingly, nitrogen compounds with either low or high carbon numbers(for a given DBE) exhibited higher reactivity than those with medium carbon numbers, which can be attributed to the low steric hindrance resulting from short alkyl chains and more naphthenic-aromatic structures, respectively. After hydrotreatment, the molecular structures of the most refractory or abundant nitrogen compounds could consist of two main types: those with multiple naphthenic-aromatic rings and those with long side chains near the nitrogen atom. This research has revealed nitrogen compounds' evolutionary mechanisms and refractory nature, and the molecular structure of the most resistant or abundant basic and neutral nitrogen compounds, providing a deeper understanding of the HDN process and ultimately paving the way for the rational RHT catalyst design and process development.
To optimize the hydrogen production efficiency of proton exchange membrane (PEM) electrolysis, a high-efficiency hybrid hydrogen production power supply, based on a 12-pulse rectification combined with an active pulse multiplication unit (APMU), is proposed. The system specifically employs a 12-pulse rectifier to manage 96.6% of the rated power, while the APMU handles the remaining component. Additionally, an optimized APMU is used to enhance original 12-pulse rectifier to 48-pulse rectifier. As a result, this hydrogen power supply demonstrates low grid-side harmonics, minimal output ripple, and high transmission efficiency. This research systematically analyzes the fundamental operating mechanisms, deriving its theoretical grid-side harmonics and output ripple, and evaluating the APMU's capacity. Finally, an experimental prototype with a 2.2 kW output power is developed to test and validate the proposed method.
To address the low-voltage, high-current requirements in hydrogen production applications, a virtual 48-pulse three-phase rectifier is proposed, and achieves the equivalent performance of four parallel 12-pulse rectifiers (12-PR). The proposed approach builds upon the conventional 12-PR design and incorporates novel asymmetric current injection units (ACIU). The ACIU is installed on the dc side of the ac-dc converter, generating a specific current at the dc link to modulate and enhance the operating modes of the 12-PR. Consequently, the 12-pulse is extended to 48, resulting in an almost sinusoidal input current with a total harmonic distortion of 3.2% and an output current with a ripple rate of 2.3%, thus significantly improving power quality. Furthermore, the asymmetric design of the current injection units eliminates the need for a phase-shifting transformer. The efficacy of the proposed rectifier for electrolytic hydrogen production is validated using a 2.2-kW experimental prototype.
The morphology-activity relationship of alumina-supported MoS2 catalysts in hydrotreating reactions remains debated, particularly concerning the role of metal clusters smaller than 2 nm versus conventional MoS2 slabs. In this work, tailored gamma-alumina support with suitable metal-support interaction (MSI) via calcination coupled with hydrothermal treatment, allowing the preparation of active phase morphologies dominated by metal clusters (Mo/gamma-Al2O3-HT-3h) or MoS2 slabs (Mo/gamma-Al2O3-HT-8h) by adjusting the sulfidation time. Aberration-corrected scanning transmission electron microscopy (Cs-STEM) and CO-FTIR spectroscopy revealed that the Mo-edge/Sedge ratio of metal cluster-dominated catalyst increases by 1.24 times compared to slab-dominated catalyst while maintaining a high sulfidation degree (Mo4+ sulfided species over 75 %). Catalytic evaluations demonstrated metal cluster-dominated catalysts have superior intrinsic hydrogenation activity (TOF = 0.20 h- 1) and quinoline hydrodenitrogenation conversion, which is attributed to the enhancement of hydrogen adsorption and dissociation behavior. These findings provide novel insights into the debated issues of morphology-activity relationships for hydrotreating catalysts, and exemplify a paradigm for optimizing catalyst performance through morphologycontrolled strategies.
Accurate bathymetry using remotely sensed data is essential for various ocean-related fields such as marine resource exploration, environmental protection and offshore development. Traditional bathymetric techniques often face limitations in high-risk areas, whereas satellitebased methods offer advantages such as low cost and extensive coverage. This work aims to integrate the complementary strengths of ICESat-2 and Sentinel-2 satellites. We propose a novel dual-distance noise reduction algorithm to extract bathymetric information from ICESat-2 data, which is then integrated with Sentinel-2 optical imagery using a U-Net deep learning model. This approach enables precise inference of nearshore bathymetric distributions. Experimental results demonstrate the efficacy of the dual-distance noise reduction algorithm in accurately identifying photon signal points, achieving an average R-2 of 0.906 and an RMSE of 0.778m in bathymetric estimation. The study provides a robust scientific basis for active-passive fusion bathymetry inversion strategies in different scenarios.
The electrical properties of the active precursor ions play an important role in the microstructure of the hydrodesulfurization (HDS) catalyst. Herein, this study first presents a simple strategy to adjust the charge of Mo-based nanoparticles (Mo-NPs) by changing the content of the organic complexing agent dodecyltrimethylammonium bromide (DTAB) and then investigates the effects of Mo-NPs with different charges on HDS catalysts. The results show that the zeta (zeta) potential of the Mo-NPs mutates from negative to positive with the DTA+/Mo molar ratio increasing to 4/7. Compared with conventional electronegative Mo precursors, the electropositive Mo-NPs could eliminate the electrostatic difference with the promoter nickel ions (Ni2+); thus, the Mo-NPs and Ni2+ could synchronously diffuse and co-load into the electropositive pore of gamma-Al2O3 by hydrothermal deposition, resulting in a more uniform distribution of active species (standard deviation of slab length = 0.51 vs. 1.05). Meanwhile, the isolating effect of amorphous carbonaceous species from the thermal decomposition of the organic complexing agent on the active phases was directly observed, and the stabilizer role was powerfully verified. Therefore, the resultant catalyst not only realized better Ni-promoted effects (synergetic factor = 7.5 vs. 5.3) but also exhibited excellent active phase morphology with much shorter length, higher stacking number and better dispersion. Finally, compared with the catalyst prepared from the conventional precursor, i.e. Mo7O246-, the Mo-NPs-derived catalyst shows the more excellent HDS activity of dibenzothiophene (reaction rate constant kHDS = 7.51 vs. 1.06 x 10-7 mol g-1 s-1; turnover frequency TOF = 5.56 vs. 1.43 h-1) and obviously enhanced HDS ratio of heavy coking diesel (99.8% vs. 96.2%). Besides, the resulting catalyst also holds a much higher HDS ratio as compared with the industrial catalyst (99.8% vs. 97.8%), showing a great potential in industrial application. The present work sheds light on the rational design of supported nanosized catalysts and provides a deeper understanding of the complicated structure-function relations. Using electropositive Mo-based nanoparticles (Mo-NPs) as precursor could realize the resulting catalyst with more uniform, shorter, higher layered, better Ni-promoted, and stable MoS2 slabs, thus holding excellent HDS performance.
Reducing hydrogen (H2) consumption massively while ensuring the ultra-strict product quality is the most critical and extremely challenging issue in diesel hydrotreating process. In this work, the effect of operating parameters (including reaction temperature, reaction pressure, hydrogen/oil (H2/oil) volume ratio and liquid hourly space velocity (LHSV)) on H2 consumption were systematically studied first. Most importantly, the reduction of H2 consumption caused by temperature elevation was calculated upon satisfying the requirements of content of sulfur (S) and polycyclic aromatic hydrocarbons (PAHs) in the diesel quality standards (S ≯10 mg/kg, PAHs ≯7%) using feedstock with different properties. Results showed that H2 consumption was reduced by 23.1% when the temperature reached 401 degrees C (compared with temperature being 365 degrees C) using a diesel feed whose S content, N content and density were 9759.1 mg/kg, 147.1 mg/kg and 0.8626 g/cm3, respectively, while the impact on the catalysts activity, structure and coke deposition behavior was relatively little which was proven by the XPS, TEM, CAT-CS and TG-MS studies on the fresh and spent sulfide catalysts. The significant reduction of H2 consumption was attributed to the different thermodynamic behavior of S and aromatic compounds at relatively high temperature which led to a slightly decrease in hydrodesulfurization (HDS) conversion while a significantly drop in hydrodearomatization (HDA) conversion. This is a promising method to effectively reduce H2 consumption which can greatly benefit the future industrial applications in producing ultra clean diesel products with ultra-low H2 consumption.
A series of related experiments were carried out based on prepared hydrocracking catalyst, Catalyst-HC. Ni & W and USY molecular sieve were selected as the hydrogenation active component and the cracking component of Catalyst-HC, respectively. Meanwhile, a kinetic model for paraffin conversion was constructed based on paraffin conversion law. Results obtained through this work indicate that the impact of H2-pressure is relatively complex. As the H2-pressure changes, the degree of hydrocracking reaction may be influenced by both hydrogen supply capacity and hydrogen proton concentration. Obtained conversion priority for three types of hydrocarbons on USY molecular sieve is as follows, aromatic ≫ cycloalkane > paraffin. Aromatic content in SRGO can affect its paraffin-retention in Hydro-D. Compared with the hydrotreating of SRGO with low aromatic content, when SRGO with relatively higher aromatic content is hydrotreated, its paraffin-retention is higher and its paraffin loss is also relatively smaller. Base on constructed model, the calculated values of SRGO-BJ conversion rate and paraffin-retention in Hydro-D are within ±10 % and ±5 % error lines, respectively. Thus, model schematic diagram is reasonable and can provide modeling reference for relevant model research.
Petroleum has played a vital role as the major supplier of materials and energy during the evolution of human civilization. Given the change in demand for energy from high to low carbon and ultimately net zero carbon, the energy framework has undergone revolutionary changes. The energy attribute of petroleum will be gradually weakened, while the material and CO2 emission attributes will be gradually strengthened. Thus, the petrochemical processing basis, scientific concepts, and ideas will undergo major adjustments to reshape the petrochemical industry. Hence, it is necessary to reconsider the evolution of the petrochemical industry from a historical perspective and to clarify the historical causes, development contexts, and possible challenges in future development. Herein, we critically reassess the key drivers and rules guiding the development of the petrochemical industry and propose a reconstruction strategy based on simplified engineering thinking, innate nature of energy and material, and CO2 emissions, which can be realized through the integration of gasification with CO as the target product and recent C1 chemistry targeting the precise synthesis of chemicals. The concept of the petrochemical industry will change from the product-based process of selection and transformation of raw material molecules to the process of carbon atom reconfiguration driven by product CO2 emissions. More accurate management of C atoms can be accomplished with greatly improved utilization efficiency and the reduction of separation intensity and CO2 emissions via the stepwise introduction of a new approach in the current petrochemical industry.
Non-thermal plasma is promising for cracking the abundant but low-quality heavy oil into value-add chemicals due to its wide feedstock adaptability and high conversion rate. In this work, heavy oil cracking characteristics by microsecond pulsed spark discharge plasma were investigated in terms of pulse voltage, pulse repetition fre-quency and discharge power. Experiment results indicate pulse voltage and pulse repetition frequency are the main factors to control product yields and distribution. Pulse voltage determines single pulse energy and in-fluences discharge stability and gas temperature. Pulse repetition frequency determines discharge intervals and affects collision reactions and quenching process. The maximum heavy oil conversion rate was 50.4% and the mass yields of H-2 and C2H2 were 3.3% and 19.7% with 10.1 W discharge power, and H-2 and C2H2 production energy consumption were 25.2 kW.h/m(3)H(2) and 55.4 kW.h/m(3)C(2)H(2). Compared with thermal plasma, heavy oil conversion rate of this work increased 12% with above 95% reduction in discharge power, and this work has a significant advantage in H-2 and C2H2 production energy consumption. Carbon nanomaterials composed of carbon nanoflakes and nanoparticles can be obtained while producing H-2 and C2H2. Especially, there were few-layers graphene nanoflakes (GNFs) in the carbon nanomaterials, which realized the full utilization of heavy oil. The possible reaction mechanism of heavy oil cracking was discussed using saturates-nucleating-aromatics-flaking theory. This work provides an effective COx-free method for one-step production of H-2, C2H2 and car -bon nanomaterials, which has wide application prospects for heavy oil utilization.
Non-thermal plasma (NTP) may be an effective and clean way for enhancing catalyst performance. The paper aims to treat the surface of catalysts by different NTP techniques. Here, radio-frequency (RF) plasma jet, dielectric barrier discharge (DBD), and spark discharge are used to treat supported bimetallic hydrogenation catalysts (i.e., Mo-Ni sulfide/γ-Al2O3 and Mo-Co oxide/γ-Al2O3) in ambient air. Surface representations of the virgin and NTPs treated catalysts show that the surface morphology, chemical states and functional groups change remarkably after NTPs treatment. The catalyst's surface become smoother after RF plasma jet treatment, but rougher after DBD or spark discharge treatment, compared with the virgin case. The heavy particles (i.e., Ar metastable states) in RF plasma jet, high-energy electrons in DBD, and heat in spark discharge play major roles in the plasma-catalyst interactions, respectively. The evident promotion of Mo chemical valence by the oxidation of O atoms happens after DBD treatment, which indicates that DBD may be an effective way to regulate Mo chemical valence. The MoS2 layers of the Mo-Ni sulfide/γ-Al2O3 catalyst are severely destroyed as the MoS2 Raman spectrum disappear after RF plasma jet treatment. The paper provides guidance for structure regulation of catalyst surfaces by NTPs.
综合介绍了多种烯烃水合反应的机理、生产工艺及催化剂的研究成果.分类详细归纳了环己烯、丙烯、高碳烯烃等通过水合反应生产相应产物醇的生产工艺和催化剂的最新研究进展,并分析了烯烃水合技术的未来发展趋势.分析发现:烯烃水合反应的路径主要分为直接路径和间接路径;其反应机理主要有马氏规则的亲电加成机理、反马氏规则的亲电加成机理、自由基反应机理等;烯烃水合反应用催化剂从液体酸、碱,过渡金属盐或氧盐,不断向分子筛、固体酸、合成树脂、光催化剂、酶催化剂方向发展.未来,光催化和生物酶催化是烯烃水合科技研究的重点方向;而反应设备参数优化、提升催化剂性能、强化物料混合效果、改善传质过程等,则是烯烃水合生产工艺优化的发展趋势.