RESUMO
Due to the high dependence on the pH of influent water and the level of ferrous species, the applicability of the electro-Fenton (EF) system is poor. A highly applicable dual-cathode (DC) EF system with self-adjusting pH and ferrous species is proposed: gas diffusion electrode (GDE) for generation H2O2 and Fe/S doped multi-walled carbon nanotubes (Fe/S-MWCNT) modification active cathode (AC) for adjusting pH and iron species. The strong synergistic enhancement effect between two cathodes (synergy factor up to 90.3%) improves the catalytic activity of this composite system about 12.4 times higher than that of cathode alone. Impressively, AC has the ability of self-regulate to shift towards the optimal Fenton pH (around 3.0) without adding reagents. Even pH can be adjusted from 9.0 to 3.4 within 60 min. This characteristic gives the system a wide range of pH applications, while avoiding the disadvantage of the high cost of traditional EF in pre-acidification. Furthermore, DC has a high and stable ferrous species supply, and the iron leaching amount is about twice less than that of heterogeneous EF system. Long-term stability of the DC system and its easy activity regeneration exhibit the potential of environmental remediation in industrial application.
Assuntos
Nanotubos de Carbono , Poluentes Químicos da Água , Peróxido de Hidrogênio , Poluentes Químicos da Água/análise , Ferro , Eletrodos , Concentração de Íons de Hidrogênio , OxirreduçãoRESUMO
Nitrogen-doped graphene as a perfectly-efficient and environmentally compatible electrocatalyst won widespread attention in electrochemical advanced oxidation processes (EAOP). However, the relationship between surface structure regulation and activity of catalysts is still lacking in systematic scientific guidance. Herein, nitrogen-doped graphene aerogel (NGA) was conveniently prepared through hydrothermal treatment, and then utilized to fabricate the gas diffusion electrode (GDE) as the cathode for tetracycline (TC) removal. High free radical yield (81.2 µM) and fast reaction rate (0.1469 min-1) were found in NGA system. The molecular dynamics simulation (MD) results showed that the interaction energy of NGA was greater than the raw graphene aerogel (GA). The adsorption activation of H2O2 and the degradation of TC occurred in the first adsorption layer of catalysts, and both processes turned more orderly after nitrogen doping. Moreover, the van der Waals interaction was stronger than the electrostatic interaction. Density function theory (DFT) revealed that the adsorption energy of H2O2 at graphitic N, pyridinic N, and pyrrolic N sites was -0.03 eV, -0.39 eV, and -0.30 eV, respectively. Pyridinic N sites were inferred as the main functional regions of in-situ activation â¢OH, there were more likely to occur ectopic reaction in pyrrolic N, and graphitic N were responsible for improving H2O2 production. By revealing the microstructure and activation characteristics of NGA, an experiment-simulation complementary strategy is provided in the EAOP to discover or to optimize new catalysts.
Assuntos
Grafite , Grafite/química , Peróxido de Hidrogênio , Simulação de Dinâmica Molecular , Oxirredução , Antibacterianos , Tetraciclina , NitrogênioRESUMO
The research object is diorite in the Lingbei TBM section of the Hanjiang-To-Weihe River Qinling tunnel, with a buried depth of over 1 km. Using MTS-2000 microcomputer-controlled electro-hydraulic servo universal testing machine and DS5-16b acoustic emission (AE) monitoring system, uniaxial compression and acoustic emission monitoring tests were carried out on rock samples, to study the uniaxial compression mechanical properties and acoustic emission characteristics of the deep diorite. The results of the study indicate that: (1) During uniaxial compression, diorite undergoes four stages: initial compaction, elasticity, yield and failure, in which the curve of the initial compaction stage is significantly smoother. The uniaxial compressive strength is 41.95 MPã102.42 MPa, with an average of 74.07 Mpa; The axial peak strain ranges from 1 % to 1.4 %, and the failure mode belongs to brittle ductile splitting failure. (2) The cumulative ringing count and energy showed a very slow increase trend during the calm period; After entering a surge period (with the appearance of Kaiser points), both show a significant transition state; During the slow increase period, the overall growth rate of the two slowed down and remained almost silent. (3) On the basis of the analysis of RA-AF values during the deformation and rupture process of diorite, it can be seen that the damage type of diorite is tensile damage by the significant low RA value and high AF value characteristics, which coincides with the actual damage fracture characteristics of the rocks in the sample. (4) During the compaction stage, there are few acoustic emission location points, which correspond to low energy and are mainly distributed at the higher and lower ends of the sample; After entering the elasticity stage, the number of positioning points significantly increases and gradually expands towards the middle; Near Kaiser point, the number of location points and corresponding energy are both in a sharp increase state, and this trend is in good agreement with the changes in the ringing count-time and energy-time curves. (5) The damage time mainly starts at the end of the calm period, and the pattern of change in the damage curve coincides with the localization point and energy evolution. The results of the research can be used as a referential basis for the development of the excavation, protection and other construction plans for the Lingbei TBM section of the Hanjiang-To-Weihe River Qinling tunnel or similar surrounding rock tunnels, as well as for further conducting triaxial unloading tests on diorite.
RESUMO
A comprehensive human health risk assessment methodology based on major hazard element screening and morphological evolution simulation is proposed. The primary targeted metal (PTM) screened by classical health risk assessment was introduced into chemical balance simulation to obtain speciation distribution and corresponding risk. According to the results of risk assessment of morphological evolution of primary targeted metal (PTM), a potential methodology for the remediation is proposed, which could reduce the risk level efficiently and quickly by changing the pH of soil environment with additional acid and alkali substances. A case study was performed in a dye factory in Suzhou city, Jiangsu Province, China. The results of classical health risk assessment showed that the regional health risk index for children exceeded tolerance value of 1, in which Cr accounted for high risk level of 61%. Chemical balance simulation results showed that CrO42- and CaCrO4 had the highest risk index, and the change of pH value would affect the proportion of CrO42- and CaCrO4 in Cr6+ ionic speciation, which may indirectly change the risk level. It is recommended to adjust the pH of the soil environment to quickly reduce regional human health risk. This study will provide a theoretical basis for public health protection and site restoration management.
Assuntos
Metais Pesados , Poluentes do Solo , Criança , China , Cidades , Monitoramento Ambiental , Humanos , Metais Pesados/análise , Medição de Risco , Solo , Poluentes do Solo/análiseRESUMO
Hydrochloride (HCl) is an acidic pollutant present in the flue gas of most municipal or hazardous waste incinerators. Hydrated lime (Ca(OH)2) is often used as a dry sorbent for injection in a spray reactor to remove HCI. However, due to the short residence time encountered, this control method has generally been found to have low conversion efficiencies which results in the high lime usage and generates large amount of fly ash as solid wastes. A fundamental study was carried outto investigate the kinetics of HCl-lime reaction under simulated flue gas conditions in order to better understand the process thereby providing a basis for an optimized lime usage and reduced fly ash production. The initial reaction rate and conversion of three limes were studied using a thermogravimetric analyzer by varying the gas flow rate, temperature (170-400 degrees C), and HCI concentrations (600-1200 mg/m3) as well as the associated particle size and surface area of the limes. The initial lime conversions were found to rely mostly on the residence time, while the ultimate lime conversions were strongly influenced by temperature and the reaction products. CaOHCI was found to be the primary product in most cases, while for one specific lime, CaCl2 was the ultimate conversion product after an extended time period. The true utilization of lime in flue gas cleanup is thus higher when CaOHCl is considered as the final product than those based on CaCl2 as the final product, which has been commonly used in previous studies. The initial reaction was controlled by diffusion of HCl in gas phase and the subsequent reaction by gaseous diffusion through the developing product layer. Increasing the HCI concentration raised the initial rate as well as conversion. However, overloading the lime with excessive HCI caused clogging at its surface and a drop in the ultimate conversion. Limes with smaller particle diameters and higher surface areas were found to be more reactive. The effect of gas-phase mass transfer was minimized when an optimum flow rate was chosen, and in the absence of internal diffusion the reaction was found to be first order with respect to HCI concentration.