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This research investigates the formation mechanism of soot and particulate matter during the pyrolysis and gasification of waste derived from Municipal Solid Waste (MSW) in a laboratory scale drop tube furnace. Compared with CO2 gasification atmosphere, more ultrafine particles (PM0.2, aerodynamic diameter less than 0.2 µm) were generated in N2 atmosphere at 1200â, which were mainly composed of polycyclic aromatic hydrocarbons (PAHs), graphitic carbonaceous soot and volatile alkali salts. High reaction temperatures promote the formation of hydrocarbon gaseous products and their conversion to PAHs, which ultimately leads to the formation of soot particles. The soot particles generated by waste derived from MSW pyrolysis and gasification both have high specific surface area and well-developed pore structure. Compared with pyrolysis, the soot generated by gasification of waste derived from MSW had smaller size and higher proportion of inorganic components. The higher pyrolysis temperature led to the collapse of the mesoporous structure of submicron particles, resulting in a decrease in total pore volume and an increase in specific surface area. Innovatively, this research provides an explanation for the effect of reaction temperature/ CO2 on the formation pathways and physicochemical properties of soot and fine particulate matter.
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Calor , Material Particulado , Pirólisis , Residuos Sólidos , Hollín , Material Particulado/análisis , Material Particulado/química , Residuos Sólidos/análisis , Hollín/análisis , Hollín/química , Eliminación de Residuos/métodos , Incineración/métodos , Dióxido de Carbono/análisis , Dióxido de Carbono/química , Hidrocarburos Policíclicos Aromáticos/análisis , Hidrocarburos Policíclicos Aromáticos/química , Tamaño de la PartículaRESUMEN
One of the primary hurdles in microdevice fabrication lies in ascertaining the most impactful tactics for adapting metal surfaces. Through a one-pot tackle and distinct mechanochemical reactions evoked by 15 min aqueous wet sand-milling (SM-15), we successfully grafted Mo-based metal-organic frameworks (Mo-MOFs) onto graphene oxides (GOs). Following this, a convenient and readily scalable methodology of electrophoretic deposition was implemented to create controllable thickness of SM-15 GOs@Mo-MOFs lubricating films, achieving considerable enhancements of 143% and 91% in hardness and Young's modulus, respectively, when compared to those of SM-15 Mo-MOFs. The successful synthesis of SM-15 GOs@Mo-MOFs was corroborated using strategies such as x-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Analyses using the micro-tribotester indicated that the new film exhibited a lowest friction coefficient of roughly 0.5 when imposed with a load of 5 N and sliding speed of 8 mm/s. In addition, the optical profiler nano-indentation in situ scanning probe microscope revealed that SM-15 GOs@Mo-MOFs films had smaller and shallower scratches and grooves compared to SM-15 Mo-MOFs ones. The calculated results of key descriptors (EHOMO, ELUMO, ΔE, etc.) in density functional theory quantitatively disclosed the interaction mechanisms between GOs@Mo-MOFs molecules and microdevices. We first scrutinized the innate properties of molecule adsorption energy and frictional mechanical behaviors using synergetic cross-scale simulations, such as Monte Carlo and finite element methods. The expectation was that this process would motivate a valuable technique for shielding in the thriving micromanufacturing.
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Plastic waste has emerged as a serious issue due to its impact on environmental degradation and resource scarcity. Plastic recycling, especially of halogen-containing plastics, presents challenges due to potential secondary pollution and lower-value implementations. Chemical recycling via pyrolysis is the most versatile and robust approach for combating plastic waste. In this Review, we present recent advancements in halogen-plastic pyrolysis for resource utilization and the potential pathways from "reducing to recycling to upcycling" halogens. We emphasize the advanced management of halogen-plastics through copyrolysis with solid wastes (waste polymers, biomass, coal, etc.), which is an efficient method for dealing with mixed wastes to obtain high-value products while reducing undesirable substances. Innovations in catalyst design and reaction configurations for catalytic pyrolysis are comprehensively evaluated. In particular, a tandem catalysis system is a promising route for halogen removal and selective conversion of targeted products. Furthermore, we propose novel insights regarding the utilization and upcycling of halogens from halogen-plastics. This includes the preparation of halogen-based sorbents for elemental mercury removal, the halogenation-vaporization process for metal recovery, and the development of halogen-doped functional materials for new materials and energy applications. The reutilization of halogens facilitates the upcycling of halogen-plastics, but many efforts are needed for mutually beneficial outcomes. Overall, future investigations in the development of copyrolysis and catalyst-driven technologies for upcycling halogen-plastics are highlighted.
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Halógenos , Plásticos , Plásticos/química , Pirólisis , Reciclaje , Residuos SólidosRESUMEN
Sulfate radical-based advanced oxidation processes (AOPs) combined biological system was a promising technology for treating antibiotic wastewater. However, how pretreatment influence antibiotic resistance genes (ARGs) propagation remains largely elusive, especially the produced by-products (antibiotic residues and sulfate) are often ignored. Herein, we investigated the effects of zero valent iron/persulfate pretreatment on ARGs in bioreactors treating sulfadiazine wastewater. Results showed absolute and relative abundance of ARGs reduced by 59.8%- 81.9% and 9.1%- 52.9% after pretreatments. The effect of 90-min pretreatment was better than that of the 30-min. The ARGs reduction was due to decreased antibiotic residues and stimulated sulfate assimilation. Reduced antibiotic residues was a major factor in ARGs attenuation, which could suppress oxidative stress, inhibit mobile genetic elements emergence and resistant strains proliferation. The presence of sulfate in influent supplemented microbial sulfur sources and facilitated the in-situ synthesis of antioxidant cysteine through sulfate assimilation, which drove ARGs attenuation by alleviating oxidative stress. This is the first detailed analysis about the regulatory mechanism of how sulfate radical-based AOPs mediate in ARGs attenuation, which is expected to provide theoretical basis for solving concerns about by-products and developing practical methods to hinder ARGs propagation.
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Genes Bacterianos , Aguas Residuales , Antibacterianos/farmacología , Farmacorresistencia Microbiana/genética , Sulfatos/farmacología , Reactores Biológicos , Óxidos de Azufre/farmacologíaRESUMEN
In the present study, novel copper-doped zirconium-based MOF (UIO-66) and copper-doped iron-based UIO-66 catalysts were prepared by hydrothermal synthesis method to improve the removal performance of gaseous benzene. The characteristics of the catalysts were analyzed by means of XRD, SEM, XPS, BET, and EPR. The copper loading catalyst had high crystallinity and irregular globular. The three kinds of catalysts with different Cu/Fe ratios had regular cubic shape. Compared with the catalyst supported with single copper, the bimetal Cu/Fe modification had a certain adjustment effect on the morphology, which specifically reflected in the uniform size and shape of catalyst particles with better dispersibility. The factors of different metal loading, dose of H2O2, and reaction temperature on benzene removal have been studied. It has been observed that in heterogeneous advanced oxidation removal of benzene, 3-Cu@UIO-66 and Cu1.5/Fe1.5@UIO-66 achieved the highest benzene removal efficiency of 81.2% and 94.6%, respectively. EPR results showed that the increase of Cu loading and different Cu/Fe ratios promoted the yield of hydroxyl radicals, thus promoted the benzene removal efficiency. The efficiency of heterogeneous oxidation removal of benzene first increased and then decreased with the increase of temperature due to H2O2 instability. DFT calculations exhibited that the Feoct-Cu-O site was a more effective activation site than the single Feoct-O site. Dissociative adsorption occurred with the O-O bond of H2O2 cracked, and the formed hydroxyls parallel adsorbed on the benzene surface. The combination of benzene and hydroxyls was strong chemisorption with the torsion angle of benzene ring obviously turned. The work was of great importance for identifying the roles of the novel catalyst for the removal of benzene pollutant from waste gases.
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Radical Hidroxilo , Hierro , Hierro/química , Peróxido de Hidrógeno/química , Cobre/química , Benceno , Circonio , Gases , Oxidación-Reducción , CatálisisRESUMEN
The synergistic activation of persulfate by multiple factors could degrade pollutants more efficiently. However, the co-activation method based on metal ions has the risk of leakage. The non-metallic coupling method could achieve the same efficiency as the metal activation and meanwhile release environmental stress. In this study, the original biochar (BC) was prepared through using Chinese medicinal residue of Acanthopanax senticosus as the precursor. Compared with other biochar, the pore size structure was higher and toxicity risk was lower. The ultrasonic (US)/Acanthopanax senticosus biochar (ASBC)/persulfate oxidation system was established for Atrazine (ATZ). Results showed that 45KHz in middle and low frequency band cooperated with ASBC600 to degrade nearly 70 % of ATZ within 50 min, and US promoted the formation of SO4- and OH. Meanwhile, the synergy index of US and ASBC was calculated to be 1.18, which showed positive synergistic effect. Finally, the potential toxicity was examined by using Toxicity Characteristic Leaching Procedure (TCLP) and luminescent bacteria. This study provides a promising way for the activation of persulfate, which is expected to bring a new idea for the win-win situation of pollutant degradation and solid waste resource utilization.
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Atrazina , Eleutherococcus , Contaminantes Químicos del Agua , Atrazina/toxicidad , Atrazina/análisis , Medicina Tradicional China , Metales , Carbón Orgánico/química , Contaminantes Químicos del Agua/análisisRESUMEN
In this work, ReaxFF molecular simulations were performed to study the pyrolysis behavior of chemical cross-linked natural rubber (NR) under non-isothermal and isothermal conditions. Three different sulfur vulcanized NR models were established and simulated to study the effect of inner sulfur structure on NR decomposition behavior and sulfur evolution in comparison with carbon cross-linked structure. To understand the NR decomposition with temperatures, the non-isothermal simulations were performed between 300 and 3800 K at a 50 K ps-1 heating rate. The results reveal that the decomposition process can be classified into four stages: 1) Structure adjustment; 2) Decomposition of the main carbon chains; 3) Secondary decomposition of heavy tar; and 4) Deep decomposition of light tar. Based on the results of non-isothermal pyrolysis, four different temperatures were selected for the isothermal simulations. Compared with carbon cross-linked NR, sulfur cross-linked structures facilitate the generation of C2H4 and C4H6 in the gas phase at low temperatures. At higher temperatures, more heavy tar is generated. Regarding the sulfur evolution, the sulfur-containing products mainly include H2S, thiophene, sulfide, and thiol. The distribution of sulfur-containing products with temperatures follows the similar pattern with the product distribution of main compounds. At higher temperatures, most sulfur exists in the form of thiophene compounds. In particular, the structure with single CS cross-links facilitates the generation of H2S at low temperatures. The results of this work provide insight into the sulfur transformation and pyrolysis behavior of vulcanized NR.
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Pirólisis , Goma , Simulación de Dinámica Molecular , Azufre , TemperaturaRESUMEN
The fate of antibiotics in activated sludge has attracted increasing interests. However, the focus needs to shift from concerning removal efficiencies to understanding mechanisms and sludge responding to antibiotic toxicity. Herein, we operated two anaerobic sequencing batch reactors (ASBRs) for 200 days with sulfadiazine (SDZ) and sulfamethoxazole (SMX) added. The removal efficiency of SMX was higher than that of SDZ. SDZ was removed via adsorption (9.91-21.18%) and biodegradation (10.20-16.00%), while biodegradation (65.44-86.26%) was dominant for SMX removal. The mechanisms involved in adsorption and biodegradation were investigated, including adsorption strength, adsorption sites and the roles of enzymes. Protein-like substance (tryptophan) functioned vitally in adsorption by forming complexes with sulfonamides. P450 enzymes may catalyze sulfonamides degradation via hydroxylation and desulfurization. Activated sludge showed distinct responses to different sulfonamides, reflected in the changes of microbial communities and functions. These responses were related to sulfonamides removal, corresponding to the stronger adsorption capacity of activated sludge in ASBR-SDZ and degradation capacity in ASBR-SMX. Furthermore, the reasons for different removal efficiencies of sulfonamides were analyzed according to steric and electronic effects. These findings propose insights into antibiotic removal and broaden the knowledge for self-protection mechanisms of activated sludge under chronic toxicities of antibiotics.
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Aguas del Alcantarillado , Sulfonamidas , Anaerobiosis , Antibacterianos , Sulfadiazina , SulfametoxazolRESUMEN
Oily sludge is a hazardous waste due to the enrichment of nitrogen, sulfur, PAHs, and heavy metals. In this work, an oily sludge from oil refining factory was pyrolyzed at various temperatures of 250-850 °C in a fixed bed reactor focusing on product distribution and migration of hazardous compounds of PAHs, sulfur, nitrogen-containing compounds, and heavy metals. The mechanism of PAHs formation and migration of nitrogen, sulfur, heavy metals were elucidated by comprehensive analysis of the solid, liquid, and gas products. The distribution and risk analysis of heavy metals were also conducted. The pyrolytic products distribution was markedly affected by pyrolysis temperatures. A maximum oil yield was observed at 500 °C, which can further crack into gas due to secondary reaction. The pyrolytic gas was enriched in the order of CO2 > CO > CH4 > H2. At lower temperatures, CO2 was largely generated due to the elimination of oxygen-containing functional groups, while H2 was mainly formed above 450 °C due to the recombination reaction. Higher temperatures promoted more N-/S-containing compounds into tar and gas phases. The N-/S-containing compounds mainly included NH3, HCN, H2S, SO2, COS in the gas phase and amines, indoles, pyridines, nitriles, thiophenes in liquid phase. PAHs with 2-ring to 5-ring were mainly generated due to the secondary reaction at higher temperatures. Moreover, Pyrolysis caused the accumulation of heavy metals in chars. Cd presented a high potential risk while the other heavy metals in chars presented a low risk.
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Metales Pesados , Pirólisis , Aceites , Aguas del Alcantarillado , TemperaturaRESUMEN
In this work, the pyrolysis of natural rubber (NR) under N2 and H2S atmosphere was performed to illustrate the possible effect of H2S on NR decomposition with and without catalysts. A molecular dynamics simulation based on reactive force field (ReaxFF) was also conducted to understand the interaction mechanism between H2S and intermediates from NR decomposition. Furthermore, the catalytic decomposition of NR under H2S atmosphere and the adsorption characteristics of H2S by zeolites alone were also carried out to investigate the effect of catalysts on sulfur behavior and the reversed effect of H2S on catalyst activity. This work revealed that the introduction of H2S can influence the yields of pyrolytic oil and gas, as well as composition of the oil. Combining experimental and simulation studies, H2S can interact with intermediates from NR decomposition forming sulfur-containing substances in pyrolytic oil. The H2S adsorption experiments by various catalysts revealed that catalysts can chemically adsorb H2S. The introduction of Zn can promote the adsorption ability by reacting with sulfur-containing substances to generate ZnS, with the desulfurization effect following the order of 3Zn/ZSM5 > ZSM5 > 3ZnO/ZSM5.
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Goma , Zeolitas , Catálisis , Pirólisis , AzufreRESUMEN
In this study, power parameters (power, frequency, and voltage), initial Hg0 concentration, and residence time are investigated for the removal of the increased Hg0 concentration via surface dielectric barrier discharge (SDBD). The synergistic effect of a Mn/Ce/Ti catalyst with SDBD is verified with a mixture of flue gas (Hg0, NO, and SO2). Results show that Hg0 oxidation efficiency has an optimal frequency, which declines as the input voltage increases. The amplification of the Hg0 removal efficiency decreases as voltage increases. The effect of the initial Hg0 concentration gradually decreases as the peak voltage increases. The residence time slightly affects the Hg0 removal efficiency at a high peak voltage. The cooling water temperature behaves differently on Hg0 oxidation under high and low voltages. X-ray photoelectron spectroscopy (XPS) reveals the relative atomic concentrations of Mn2+ and Mn3+ in the Mn-TiO2 and Mn-Ce-TiO2 catalysts are 66.84% and 65.80%, respectively, which indicate that Ce addition will not affect surface Mn. Mn has a limited catalytic action on the removal of flue gas with and without SDBD. Nevertheless, SDBD can stimulate the oxygen storage capacity of Mn to increase the NO2 conversion rate. Mn-Ce-TiO2 greatly improves the removal efficiencies of NO and SO2 because of the existence of the redox pairs of Mn4+/Mn3+, Ce4+/Ce3+, and Ti4+/Ti3+. However, the three catalysts slightly differ on Hg0 removal when combined with SDBD, indicating that the effect of the catalyst was weakened after SDBD was added.
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Mercurio , Titanio , Catálisis , Oxidación-Reducción , TemperaturaRESUMEN
This work showcases cost-effective elemental mercury capture strategy enabled by bamboo saw dust and bromine flame retardant (BFR) derived sorbent prepared by a novel hydrothermal-pyrolysis method. The hydrothermal treatment of bamboo and BFR blend was conducted in subcritical water resulting in a hydrothermal char. Subsequently, the hydrothermal char was pyrolyzed in nitrogen atmosphere leading to an improved pore architecture. The resulting biomaterials were proven highly effective for Hg removal. A thorough analysis of the physicochemical properties of the samples was conducted by means of BET, SEM, XRD, XPS and FT-IR. Key parameters such as bamboo/BFR ratio, hydrothermal temperatures and pyrolysis temperatures influence Hg0 removal capacity of our bio-sorbents. Overall, the optimal bamboo/BFR ratio, hydrothermal temperature and pyrolysis temperature are 2:1, 320 °C and 800 °C, respectively. Under these optimized conditions, a very promising elemental mercury removal efficiency of 99% is attained. The kinetics and mechanism of Hg0 removal are also proposed. The experimental data fit well with a pseudo-second-order model, indicating that Hg0 adsorption over sorbents was dominated by chemisorption. Our results indicate that the C-Br groups in sorbents provide active sites for oxidizing Hg0 into HgBr2.
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Novel hydroxylated UIO-66 for gaseous elemental mercury (Hg0) removal has been considered to be an emerging method because of its economical and reusable property. Density functional theory studies were investigated to reveal the enhanced heterogeneous interaction mechanisms between mercury and hydroxylated UIO-66 with and without the presence of H2O2 vapor. The adsorption and dissociation of H2O2 and the generation mechanism of surface hydroxyls on UIO-66 were investigated. Results indicated that H2O2 preferred to disconnect the O-O bond followed by the generation of two hydroxyls in the presence of H2O2. The hydroxyl adsorbed on UIO-66 and formed the UIO-66 hydroxylation product. The interaction performances between Hg0, H2O2, and UIO-66 as well as the interaction performances between Hg0 and hydroxylated UIO-66 systems were both evaluated through binding energy and the Mulliken charge analysis. Interacted energies indicated thermodynamically favorable processes of Hg-OH formation on hydroxylated UIO-66. The Mulliken charge changes revealed an oxidative process of mercury.
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Mercurio , Adsorción , Gases , Peróxido de Hidrógeno , Oxidación-ReducciónRESUMEN
Simultaneous removal of NOx and SO2 is carried out by an oxidation-absorption process, which NO oxidized by active hydroxyl radicals (·OH) derived from catalytic decomposition of vaporized H2O2 over Fe3O4/TiO2 and then adsorbed by NaOH solution along with SO2. Fe3O4/TiO2 synthesized by wet impregnation method with an additional reduction under H2 atmosphere was characterized by XRD, FTIR, BET, XPS, and VSM analysis. Effects of H2O2 concentration, H2O2 injection rate, reaction temperature, gas flow rate, and flue gas component on simultaneous removal were investigated. The experimental results show that NO can be effectively oxidized by highly reactive ·OH radicals generated from H2O2 decomposition over Fe3O4/TiO2 catalyst, and removal efficiencies of 93.31% for NO, 85.90% for NOx, and 100% for SO2 were obtained. The surface zero-valent iron (Fe0) and divalent iron (Fe2+) are the key factors of the catalytic oxidation with hydroxyl radical. H2O2 adsorption and dissociation mechanism on catalyst surface was studied using DFT calculation. The calculation results demonstrate that H2O2 prefers to dissociate on iron containing surface, and ·OH radicals generation follow by Haber-Weiss (H-W) mechanism. The stable oxidative product of HNO2 and HNO3 were generated through NO/NO2 and H2O2 co-adsorption on the FeO/TiO2 (0 0 1) surface.
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Peróxido de Hidrógeno , Hierro , Catálisis , Oxidación-Reducción , TitanioRESUMEN
A computer casing plastic waste containing brominated flame retardants (BFRs) was pyrolyzed in a two-stage vertical quartz tube reactor using iron and nickel metals modified MCM-41 catalysts. Various catalysts with different ratios of Fe and Ni were prepared and utilized to study their catalytic performance. At the presence of 20%Ni/MCM-41 catalyst, the pyrolytic yield of oil and gas reached maximum values of 49.9 wt% and 13.8 wt% respectively. The co-existence of Fe and Ni showed synergistic effect on oil composition by promoting the formation of valuable single ring hydrocarbons. With regard to the 15%Fe-5%Ni/MCM-41, 10%Fe-10%Ni/MCM-41 and 5%Fe-15%Ni/MCM-41 catalysts, the production of single ring hydrocarbons were 64.58%, 65.93% and 64.74% respectively. The bimetallic catalysts also exhibited remarkable effect on eliminating bromine from pyrolytic oil. At the presence of Fe-Ni/MCM-41, the bromine in pyrolytic oil was reduced to below 4 wt% compared with 10 wt% without catalyst. Higher amounts of Fe in the catalyst is beneficial for the debromination efficiency. The debromination process by the Fe-Ni/MCM-41 may be realized by these different mechanisms: catalytic cracking of organobromines, reaction of loaded metal oxides with HBr/SbBr3, and deposition of organobromines on the surface of catalyst.
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Plásticos/análisis , Eliminación de Residuos/métodos , Bromo , Catálisis , Hierro , Níquel , Óxidos , Pirólisis , Dióxido de SilicioRESUMEN
The performance of selective catalyst reduction systems highly depends on the degree of mixing between NH3 and NOx and the flow uniformity of velocity and concentration, which are sensitive to several parameters such as the installment of gate leafs, a hybrid grid, a straightener, and the ammonia injection method. In this work, computational fluid dynamics was applied to investigate these parameters in heat recovery steam generators. Performance of gate leafs and a new type of hybrid grid was considered. Analyses showed that gate leafs significantly improved the uniformity of velocity distribution and that the new type of hybrid grid improved the uniformity of concentration distribution. The velocity relative standard deviation decreased from 19.6% to 5.4%, and the concentration relative standard deviation decreased from 70% to 12.7%. Experiments also qualitatively confirmed the reliability of simulation results. Moreover, the hybrid grid was optimized with different structures. Results indicated that a 30° crossed angle could obtain a better mixing between NH3 and NOx with a slight decrease in pressure. In addition, an optimal injection method of the ammonia injection grid was designed, and it was helpful in conducting the field operation. The relationship between the thickness of the straightener and the incident angle at the entrance of catalyst layer was discussed.
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Amoníaco , Desnitrificación , Catálisis , Hidrodinámica , Reproducibilidad de los ResultadosRESUMEN
Elemental mercury (Hg0) emitted from coal-fired power plants and municipal solid waste (MSW) incinerators has caused great harm to the environment and human beings. The strong oxidized â¢OH radicals produced by UV/H2O2 advanced oxidation processes were studied to investigate the performance of Hg0 removal from simulated flue gases. The results showed that when H2O2 concentration was 1.0 mol/L and the solution pH value was 4.1, the UV/H2O2 system had the highest Hg0 removal efficiency. The optimal reaction temperature was approximately 50 °C and Hg0 removal was inhibited when the temperature was higher or lower. The yield of â¢OH radicals during UV/H2O2 reaction was studied by electron paramagnetic resonance (EPR) analysis. UV radiation was the determining factor to remove Hg0 in UV/H2O2 system due to â¢OH generation during H2O2 decomposition. SO2 had little influence on Hg0 removal whereas NO had an inhibitory effect on Hg0 removal. The detailed findings for Hg0 removal reactions over UV/H2O2 make it an attractive method for mercury control from flue gases.
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Contaminantes Atmosféricos/aislamiento & purificación , Peróxido de Hidrógeno/química , Mercurio/aislamiento & purificación , Rayos Ultravioleta , Carbón Mineral , Espectroscopía de Resonancia por Spin del Electrón , Diseño de Equipo , Gases/química , Incineración , Oxidación-Reducción , Centrales Eléctricas , Residuos Sólidos , TemperaturaRESUMEN
A novel technique for photocatalytic removal of elemental mercury (Hg(0)) using visible-light-driven Ag/AgBr-Ag2CO3 hybrids was proposed. The ternary Ag/AgBr-Ag2CO3 hybrids were synthesized by a simple modified co-precipitation method and characterized by N2 adsorption-desorption, scanning electron microscope (SEM), X-ray diffraction (XRD), UV-vis diffused reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) techniques. The effects of AgBr content, fluorescent lamp (FSL) irradiation, solution temperature, SO2 and NO on Hg(0) removal were investigated in detail. Furthermore, a possible reaction mechanism for higher Hg(0) removal was proposed, and the simultaneous removal of Hg(0), SO2 and NO was studied. The results showed that a high efficiency of Hg(0) removal was obtained by using Ag/AgBr-Ag2CO3 hybrids under fluorescent lamp irradiation. The AgBr content, FSL irradiation, solution temperature, and SO2 all exhibited significant effects on Hg(0) removal, while NO had slight effect on Hg(0) removal. The addition of Ca(OH)2 demonstrated a little impact on Hg(0) removal and could significantly improve the SO2-resistance performance of Ag/AgBr(0.7)-Ag2CO3 hybrid. The characterization results exhibited that hydroxyl radical (OH), superoxide radical (O2(-)), hole (h(+)), and Br(0), were reactive species responsible for removing Hg(0), and the h(+) played a key role in Hg(0) removal.
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This work aims to study the mechanism of heavy metals vaporization by MgCl2â 6H2O. Firstly, the decomposition mechanism of MgCl2â 6H2O was investigated by thermodynamic equilibrium calculations, XRD and TG. Upon heating, MgCl2â 6H2O went through the processes of dehydration and hydrolysis simultaneously accompanied by the release of HCl between 150 and 500°C. At temperature higher than 500°C, Mg(OH)Cl gradually release part of HCl. MgCl2â 6H2O followed the similar processes of decomposition at both oxidative and reductive atmospheres. In oxidative atmosphere, vaporization of Zn and Cu was significantly accelerated by MgCl2â 6H2O. However, in inert atmosphere, vaporization of Cu was not promoted since copper chloride was only stable in oxidative atmosphere. Under slow heating condition, vaporization of heavy metals were close to that under fast heating condition. This may be partially attributed to that most heavy metals already reacted with HCl forming metal chlorides below 500°C, which can be vaporized at higher temperature. Moreover, the Mg(OH)Cl contributed to release HCl up to 800°C. At such high temperature, the metal chlorides continue to be formed and then vaporized. After treatment, the leaching concentration of heavy metals from treated fly ashes were much lower than that from raw fly ash and met the regulatory limit of leachate. Since a large amount of MgSiO3 were formed during thermal treatment, the fly ash treated with MgCl2â 6H2O can be used as raw materials for glass-ceramics production.
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Ceniza del Carbón/química , Cloruro de Magnesio/química , Metales Pesados/química , Residuos Sólidos , Ceniza del Carbón/toxicidad , Ácido Clorhídrico/química , Incineración , Temperatura , Termodinámica , Volatilización , Difracción de Rayos XRESUMEN
Laboratory experiments were conducted to investigate the volatilization behavior of heavy metals during pyrolysis and combustion of municipal solid waste (MSW) components at different heating rates and temperatures. The waste fractions comprised waste paper (Paper), disposable chopstick (DC), garbage bag (GB), PVC plastic (PVC), and waste tire (Tire). Generally, the release trend of heavy metals from all MSW fractions in rapid-heating combustion was superior to that in low-heating combustion. Due to the different characteristics of MSW fractions, the behavior of heavy metals varied. Cd exhibited higher volatility than the rest of heavy metals. For Paper, DC, and PVC, the vaporization of Cd can reach as high as 75% at 500 °C in the rapid-heating combustion due to violent combustion, whereas a gradual increase was observed for Tire and GB. Zn and Pb showed a moderate volatilization in rapid-heating combustion, but their volatilities were depressed in slow-heating combustion. During thermal treatment, the additives such as kaolin and calcium can react or adsorb Pb and Zn forming stable metal compounds, thus decreasing their volatilities. The formation of stable compounds can be strengthened in slow-heating combustion. The volatility of Cu was comparatively low in both high and slow-heating combustion partially due to the existence of Al, Si, or Fe in residuals. Generally, in the reducing atmosphere, the volatility of Cd, Pb, and Zn was accelerated for Paper, DC, GB, and Tire due to the formation of elemental metal vapor. TG analysis also showed the reduction of metal oxides by chars forming elemental metal vapor. Cu2S was the dominant Cu species in reducing atmosphere below 900 °C, which was responsible for the low volatility of Cu. The addition of PVC in wastes may enhance the release of heavy metals, while GB and Tire may play an opposite effect. In controlling heavy metal emission, aluminosilicate- and calcium-based sorbents can be co-treated with fuels. Moreover, pyrolysis can be a better choice for treatment of solid waster in terms of controlling heavy metals. PVC and Tire should be separated and treated individually due to high possibility of heavy metal emission. This information may then serve as a guideline for the design of the subsequent gas cleaning plant, necessary to reduce the final emissions to the atmosphere to an acceptable level.