Effective degradation of quinoline by catalytic ozonation with MnCexOy catalysts: performance and mechanism.

Quinoline inevitably remains in the effluent of coking wastewater treatment plants due to its bio-refractory nature, which might cause unfavorable effects on human and ecological environments. In this study, MnCexOy was consciously synthesized by α-MnO2 doped with Ce3+ (Ce:Mn = 1:10) and employed as the ozonation catalyst for quinoline degradation. After that, the removal efficiency and mechanism of quinoline were systematically analyzed by characterizing the physicochemical properties of MnCexOy, investigating free radicals and monitoring the solution pH. Results indicated that the removal rate of quinoline was greatly improved by the prepared MnCexOy catalyst. Specifically, the removal efficiencies of quinoline could be 93.73, 62.57 and 43.76%, corresponding to MnCexOy, α-MnO2 and single ozonation systems, respectively. The radical scavenging tests demonstrated that •OH and •O2- were the dominant reactive oxygen species in the MnCexOy ozonation system. Meanwhile, the contribution levels of •OH and •O2- to quinoline degradation were about 42 and 35%, respectively. The abundant surface hydroxyl groups and oxygen vacancies of the MnCexOy catalyst were two important factors for decomposing molecular O3 into more •OH and •O2-. This study could provide scientific support for the application of the MnCexOy/O3 system in degrading quinoline in bio-treated coking wastewater.

Evaluation of metal pollution characteristics using water and moss in the Luanchuan molybdenum mining area, China.

Luanchuan is rich in molybdenum resources, and mining activities are frequent, but over-mining can cause serious metal pollution to the local environment. To explore the degree of metal pollution caused by mining activities, the content characteristics and spatial distribution of metals in mining areas were studied by measuring the concentrations of Fe, Mn, Zn, Ba, Mo, Cu, Cr, Co, V, and W in surface water and mosses of mining areas. In addition, the metal pollution index (HPI), contamination factor (CF), and pollution load index (PLI) were used to evaluate metal pollution, and factor analysis was used to analyze the sources of metals. The results of the analysis of surface water at the mine site indicate the most abundant element in surface water, with a maximum concentration of 3713.8 µg/L, and its content far exceeds the water quality standard of Class III of the Environmental Quality Standard for Surface Water. The results of the HPI analysis showed that nearly 90% of the surface water was moderately contaminated (HPI ≥ 15). The results of the analysis of atmospheric deposition at the mine site confirm that the metal elements with a high threat to the atmospheric environment are Mo and W. The results of PLI indicate that the level of atmospheric deposition pollution in the study area is severe (PLI > 4). Factor analysis indicated that rock weathering and mining activities were the main sources of metals. This study provides a theoretical basis for the investigation and control of metal pollution in similar metal mining areas.

Photocatalytic Degradation of Gaseous Benzene Using Cu/Fe-Doped TiO2 Nanocatalysts under Visible Light.

Visible-light-enhanced TiO2 nanocatalysts doped with Cu and Fe were synthesized using the sol-gel method to investigate their performance in degrading gaseous benzene. The structure and morphology of mono- and co-doped TiO2 (i.e., Cu/Fe-TiO2, Cu-Fe-TiO2) were characterized using SEM, EDS, XRD, BET, Raman, UV-vis-DRS, and XPS techniques. The results indicated that the presence of Cu/Fe mono- and co-doped TiO2 leads to the formation of an anatase phase similar to pure TiO2. Furthermore, the introduction of Cu/Fe enhanced the presence of lattice defects and increased the specific surface area of TiO2. This enhancement can be attributed to the increase in oxygen vacancies, especially in the case of Cu-Fe-TiO2. Additionally, Cu-Fe-TiO2 showed a higher concentration of surface-bound hydroxyl groups/chemically adsorbed oxygen and a narrower bandgap than pure TiO2. Consequently, Cu-Fe-TiO2 exhibited the highest photocatalytic performance of 658.33 µgC6H6/(g·h), achieving a benzene degradation rate of 88.87%, surpassing that of pure TiO2 (5.09%), Cu-TiO2 (66.92%), and Fe-TiO2 (59.99%). Reusability tests demonstrated that Cu-Fe-TiO2 maintained a high benzene degradation efficiency of 71.4%, even after five experimental cycles, highlighting its exceptional stability and reusability. In summary, the addition of Cu/Fe to TiO2 enhances its ability to degrade gaseous benzene by prolonging the catalyst's lifespan and expanding its photoresponse range to include visible light.

Investigation on the gaseous benzene removed by photocatalysis employing TiO2 modified with cobalt and iodine as photocatalysts under visible light.

A new type of photocatalysts, nanocrystalline titanium dioxide (TiO2) doped with Co and I, were synthesized and modified via the sol-gel method to enhance the utilization of visible light. Herein, mono- and co-doped TiO2 (i.e. Co-TiO2, I-TiO2, Co-I-TiO2) were employed as the photocatalysts to investigate the photocatalytic performance on gaseous benzene removal. The prepared photocatalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET)-specific surface areas, Raman spectroscopy, UV-visible diffuse reflectance spectroscopy (UV-vis-DRS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and electrochemical impedance spectroscopy (EIS). Results indicated that both particle sizes and band gaps of TiO2 were significantly reduced by doping with Co/I. Also, the lattice defects and the specific surface areas of TiO2 were substantially augmented by adding Co/I because of the increase of oxygen vacancies, especially for Co-I-TiO2. Meanwhile, Co and I were distributed on the titanium base with the existence of multivalent states. The benzene treatment capacity of Co-I-TiO2, Co-TiO2, I-TiO2 and Pure TiO2 is 441.46, 424.36, 388.06, and 51.25 µgC6H6/(g·h), respectively. To sum up, photocatalytic degradation of gaseous benzene could be improved by doping with Co/I because of the extension of catalyst lifetime and light response range covering visible light.

Improvement of Cu2 ZnSn(S,Se)4 Solar Cells by Adding N,N-Dimethylformamide to the Dimethyl Sulfoxide-Based Precursor Ink.

Cu2 ZnSn(S,Se)4 (CZTSSe) solar cells based on dimethyl sulfoxide (DMSO) Cu-Zn-Sn-S precursor ink have seen tremendous progress in recent years. However, the wettability between the ink and Mo substrate is poor, owing to the high viscosity of the highly concentrated Cu-Zn-Sn-S ink. Herein, a solvent engineering process is proposed in which N,N-dimethylformamide (DMF) is added into the DMSO-based Cu-Zn-Sn-S ink for the deposition of CZTSSe thin-film absorbers in air. The addition of DMF significantly improves the wettability between the precursor ink and Mo substrate. The DMF/(DMF+DMSO) ratio also plays a critical role in determining the crystal quality of the resulting CZTSSe absorber and the device performance. The grain size of CZTSSe thin films increases with increasing DMF/(DMF+DMSO) ratio. Particularly, large grains through the whole cross section can be achieved with 20 % DMF addition. Accordingly, the power conversion efficiency of the device increases from 6.5 % to 8.6 % under AM 1.5G illumination. However, the efficiency decreases to 5.4 % when the DMF content is further increased to 30 %. Interface recombination and back contact barrier are found to be the main limitations of these devices.

New insight of ozone pollution impact from flare emissions of chemical plant start-up operations.

Flaring is a common and necessary operation for chemical industries, which is designed to manage dangerous process overpressure scenarios or to release and destroy off-spec products during chemical plant upsets or turnarounds. However, excessive flaring can emit large quantities of VOCs and NOx into the atmosphere, which will cause transient and localized ozone pollution events in the presence of sunlight. The objective of this study was to quantify the impact to regional air-quality due to flare emissions from chemical plant start-up operations through the coupling of dynamic process simulations via Aspen Plus and air-quality simulations via CAMx. Simulation results from case studies have indicated that the corresponding ozone increments can vary significantly from 0.2 ppb to 17.8 ppb under different temporal and spatial factors, including the start-up starting hour, starting day, and plant location. Additional ozone sensitivity simulations have also indicated that the corresponding ozone increments are higher when the plant is located in a VOC-limited area than that in a NOx-limited area. The results from this study have delivered a cost-effective air-quality control practice for plant start-ups with a minimum air-quality impact through selecting the optimal starting time within the allowable ranges. The practice has significant potential to benefit all stakeholders, including environmental agencies, chemical industries, and local communities.

Study on regional air quality impact from a chemical plant emergency shutdown.

Emergency shutdowns of chemical plants (ESCP) inevitably generate intensive and huge amounts of VOCs and NOx emissions through flaring that can cause highly localized and transient air pollution events with elevated ozone concentrations. However, quantitative studies of regional ozone impact due to ESCP, in terms of how ESCP would affect and to what extent ESCP could impact, are still lacking. This paper reports a systematic study on regional air quality impact from an olefin plant emergency shutdown due to the sudden failure of its cracked gas compressor (CGC). It demonstrates that emergency shutdown may cause significant ozone increment subject to different factors such as the starting time of emergency shutdown, flare destruction and removal efficiency (DRE) and plant location. In our studied case, the 8-hr ozone increment ranges from 0.4 to 3.3 ppb under different starting time, from 3.3 to 24.8 ppb under different DRE, and from 1.6 to 3.3 ppb under different locations. The results enable us to understand how and to what extent emergency operating activities of the chemical process will affect local air quality, which might be beneficial for decision makings on emergency air-quality response and control in the future.