RESUMO
Iron-doped biochar has been widely used as an adsorbent to remove contaminants due to the high adsorption performance, but it still suffers from complicated preparation methods, unstable iron loading, unsatisfactory specific surface area, and uneven distribution of active sites. Here, a novel magnetic porous biochar (FeCS800) with nanostructure on surface was synthesized by one-pot pyrolysis method of corn straw with K2FeO4, and used in orange G (OG) and tetracycline (TC) adsorption. FeCS800 exhibited outstanding adsorption capacities for OG and TC after K2FeO4 activation and the adsorption data were fitted satisfactorily to Langmuir isotherm and Pseudo-second-order kinetic model. The maximum adsorption capacities of FeCS800 for OG and TC were around 303.03 mg/g and 322.58 mg/g, respectively, at 25 °C and pH 7.0, which were 16.27 and 24.61 times higher than that before modification. Thermodynamic studies showed that the adsorption of OG/TC by FeCS800 were thermodynamically favorable and highly spontaneous. And the adsorption capacity of OG and TC by FeCS800 remained 77% and 81% after 5 cycles, respectively, indicating that FeCS800 had good stability. The outstanding adsorption properties and remarkable reusability of FeCS800 show its great potential to be an economic and environmental adsorbent in contaminants removal.
Assuntos
Carvão Vegetal , Tetraciclina , Poluentes Químicos da Água , Adsorção , Tetraciclina/química , Carvão Vegetal/química , Poluentes Químicos da Água/química , Porosidade , Compostos Azo/química , Benzenossulfonatos/química , Cinética , TermodinâmicaRESUMO
Graphene is one of the most promising thermal protection materials for high-speed aircraft due to its lightweight and excellent thermophysical properties. At high Mach numbers, the extremely high postshock temperature would dissociate the surrounding air into a mixture of atomic and molecular components in a highly thermochemical nonequilibrium state, which greatly affects the subsequent thermal chemical reactions of the graphene interface. Through establishing a reactive gas-solid interface model, the reactive molecular dynamics method is employed in this study to reveal the influences of the thermochemical nonequilibrium gas mixture on the thermal oxidation and nitridation mechanisms of graphene sheet. The results show that three distinctive stages can be recognized during bombardment of various nonequilibrium gas components toward the graphene sheet: (i) collision and surface adsorption stage, (ii) gas-solid heterogeneous reaction stage, and (iii) gas phase homogeneous reaction stage. The surface catalysis effect is found to be dominant during the first two stages, which can influence the following ablation behavior of graphene significantly at high-temperature conditions. Moreover, surface catalysis, oxidation, nitridation, and ablation mechanisms between nonequilibrium gas and graphene interface are revealed, which is of high relevance for future interfacial design and application of graphene as a thermal protection material.
RESUMO
This study synthesized novel magnetic biochar (PCMN600) by KMnO4-NaOH combined modification using iron-containing pharmaceutical sludge to remove toxic metals from wastewater effectively. Various characterization experiments of engineered biochar showed that the modification process introduced ultrafine MnOx particles on the carbon surface and resulted in higher BET surface area and porosity along with more oxygen-containing surface functional groups. Batch adsorption studies indicated that the maximum adsorption capacities of PCMN600 for Pb2+, Cu2+ and Cd2+ were 181.82 mg/g, 30.03 mg/g and 27.47 mg/g, respectively, at a temperature of 25 °C and pH of 5.0, which were much higher than that of pristine biochar (26.46 mg/g, 6.56 mg/g and 6.40 mg/g). The adsorption datums of three toxic metal ions fitted well to the pseudo-second-order model and Langmuir isotherm, and the sorption mechanisms were identified as electrostatic attraction, ion exchange, surface complexation, cation-π interaction and precipitation. The strong magnetic properties of the engineered biochar endowed the adsorbent with remarkable reusability, and after five cycles of recycling, PCMN600 still retained nearly 80% of its initial adsorption capacities.
RESUMO
The penicillin industry produces a large amount of penicillin mycelial dreg (PMD), potentially causing severe environmental problems without proper treatment and disposal. To achieve the goals of PMD management, the present work explored the potential of PMD as a novel feedstock to produce biochar with very high adsorption performance. PMD was pyrolyzed at 400-800 °C to prepare biochars (PMD-BCs), and the physical and chemical properties were characterized using various methods. The adsorption capacities of Pb2+ on PMD-BC400, PMD-BC600, and PMD-BC800 were 37.04, 62.89, and 107.53 mg/g, respectively, at a temperature of 25 °C and pH of 5.0. The adsorption process of Pb2+ on PMD-BCs can be well described by the Langmuir model and pseudo-second-order model. Mineral precipitation, ion exchange, functional group complexation and Pb2+-π interaction were involved in the adsorption of Pb2+ on PMD-BCs. Moreover, mineral precipitation and ion exchange dominated Pb2+ sorption on PMD-BCs (84.71-92.73%). This study indicates the transition of PMD to biochar for Pb2+ adsorption is a promising method for PMD utilization.
Assuntos
Pirólise , Poluentes Químicos da Água , Chumbo , Resíduos Perigosos , Penicilinas , Carvão Vegetal/química , Adsorção , Minerais , Cinética , Poluentes Químicos da Água/análiseRESUMO
A deep understanding of surface catalysis recombination characteristics is significant for accurately predicting the aeroheating between hypersonic non-equilibrium flow and thermal protection materials, while a de-coupling sensitivity analysis of various influential factors is still lacking. A gas-solid interface (GSI) model with a hyperthermal flux boundary was established to investigate the surface catalysis recombination mechanisms on nanoscale silica surfaces. Using the reactive molecular dynamics (RMD) simulation method, the effects of solid surface temperature, gas incident angle, and translational energy on the silica surface catalysis recombination were qualified under hyperthermal atomic oxygen (AO), atomic nitrogen (AN), and various AN/AO gas mixtures' influence. It can be found that, though the Eley-Rideal (E-R) recombination mechanism plays a dominant role over the Langmuir-Hinshelwood (L-H) mechanism for all the sensitivity analyses, a non-linear increasing pattern of AO recombination coefficient γO2 with the increase in incident angle θin and translational energy Ek is observed. Compared with the surface catalysis under hyperthermal AO impact, the AN surface adsorption fraction shows an inverse trend with the increase in surface temperature, which suggests the potential inadequacy of the traditional proportional relationship assumptions between the surface adsorption concentration and the surface catalysis recombination coefficient for other species' impact instead of AOs. For the incoming bi-component AO/AN gas mixtures, the corresponding surface catalysis coefficient is not the simple superposition of the effects of individual gases but is affected by both the intramolecular bond energies (e.g., O2, N2) and intermolecular energies (e.g., Si/N, Si/O).
RESUMO
Improperdisposal of sludge will release heavy metals contained in sludge into soils or waters which could further move through the food chain, posing a risk to human health. Understanding the transformation and stabilization of heavy metals (HMs) during pyrolysis is of great value for safe disposal of sludge. Herein, municipal sewage sludge (MSS, organic-dominated) and pharmacy sludge (PS, inorganic-dominated) were pyrolyzed to investigate the effects of organic and inorganic components and temperature on the stabilization of HMs in sludges. The results showed that pyrolysis can promote the transition of HMs from mobile fractions to stable fractions. Compared to MSS and PS, the potential ecological risk index of biochar derived from MSS and PS decreased by 95.51% and 85.05%, respectively, after pyrolysis at 800 °C. The stabilization of HMs in MSS was mainly due to the complexation reactions between metals and amide functional groups (-CO-NH-) during pyrolysis. Moreover, the mechanism of HMs stabilization in PS lied in the formation of a stable crystal-structure such as copper iron oxide (Cu6Fe3O7) and copper iron phosphate (Cu2Fe5(PO4)6, Cu3Fe4(PO4)6) with iron-containing minerals after high-temperature pyrolysis. The results of this study indicated that the organic and inorganic components of sludge play different roles in the stabilization and transformation of HMs during pyrolysis, which provided a scientific basis for the ecotoxicity reduction of HMs and safe disposal of sludge.
Assuntos
Metais Pesados , Pirólise , Carvão Vegetal , Humanos , Ferro , Metais Pesados/análise , Esgotos/química , SoloRESUMO
The pyrolysis characteristics, kinetics, and evolved gas analysis of chrome-tanned sludge were investigated by thermogravimetry (TG) with Fourier-transform infrared spectroscopy (TG-FTIR) and pyrolysis with gas chromatography and mass spectrometric detection (Py-GC/MS). Friedman, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) methods were used to calculate kinetic parameters in the kinetic study. The chrome-tanned sludge contained 7600â¯mgâ¯kg-1 Cr in the form of CrOOH and 41,400â¯mgâ¯kg-1 S in the form of S8. The activation energy derived by Friedman method increased from 139.83 to 590.72â¯kJâ¯mol-1 as the temperature increased from 50 to 500⯰C, much higher than those of lignocellulosic biomass and sewage sludge. The TG-FTIR results showed that the main component of the pyrolysis gases was organics that contained alkane groups, and this component reached a maximum at â¼500⯰C. The Py-GC/MS results indicated that the diesel-range organics (C10-C28) accounted for more than 65% of the evolved gases; 20%-31% of the evolved gases were C16 and C18, and included mainly palmitic, stearic, and oleic acids. The evolved gases contained high contents of sulfur and nitrogen compounds, mainly in the forms of elemental sulfur (S6 and S8) and nitriles, respectively. Kinetics and evolved gases determining provide a better understanding of tanned sludge pyrolysis and references for pyrolysis reactor design and scale-up.