Circulating Flow-Electric-Field-Configuration-Enhanced Cadmium Cementation from Sulfate Systems and Its Optimization Mechanism.

In this work, a novel flow-electric field coupling configuration was designed and implemented for enhancing Zn-Cd cementation. A series of tests was conducted to explore the optimization of the Zn-Cd cementation process and its mechanism. Firstly, the various characteristics of the sponge cadmium at various locations in the device were compared, and it was concluded that the optimum purity of the sponge cadmium obtained from the anode was up to 94.1%. The generation and stripping of the cadmium sponge was revealed for the first time by cross-sectional electron microscopy. The four stages of the apparent reaction in the system were analyzed in relation to the pH, cadmium concentration and cadmium sponge flaking at each flow rate. It was proved that the separation of cadmium sponge mainly occurred in the third phase. Secondly, by comparing the morphology and specific surface area of the cadmium sponge at different flow rates, the optimum flow field velocity was identified as 30 mL/s. At this point, the specific surface area reached a maximum of 1.151 m2/g. Six flow field configurations were compared and preferred. The results demonstrated that the LCAH (Low-Cathode-Anode-High) modulation resulted in a sparser structure of the cadmium sponge, which was more easily exfoliated from the zinc anode surface by fluid impact. This was considered to be the most beneficial flow field configuration for improving the cadmium cementation rate and reducing the cost of the reaction. Moreover, the reaction steps of the system were analyzed. Its rate-limiting step was initially empirically identified as the diffusion step and proven by calculating the activation energy of 12.6 kJ/mol. It was confirmed that the diffusion process under different flow field configurations followed the first-order kinetic principle. In addition, the system's reaction phases were compared. Calculations confirmed that the diffusion process under various flow field configurations followed first-order kinetics. The diffusion coefficient of LACH proved to be the highest in the comparative tests, and the evident experimental results supported this conclusion.

Preparation of Heavy Metal Trapping Flocculant Polyacrylamide-Glutathione and Its Application for Cadmium Removal from Water.

In this study, a heavy metal trapping gel with multiple ligand groups was prepared for the first time using response surface methodology. The gel was produced by condensing and grafting glutathione as a grafting monomer onto the main polyacrylamide chain, based on the Mannich reaction mechanism with formaldehyde. FTIR, SEM, TG-DSC, and zeta potentials were used to characterize the gel. The results demonstrated that the gel was morphologically folded and porous, with a net-like structure, which enhanced its net trapping and sweeping abilities, and that glutathione was used to provide sulfhydryl groups to boost the metal trapping ability of polyacrylamide. Coagulation experiments showed that the highest efficiency of the removal of Cd ions from water samples was achieved when the concentration of polyacrylamide-glutathione was 84.48 mgL-1, the concentration of Cd was 10.0 mgL-1, the initial turbidity was 10.40 NTU, and the initial pH was 9.0. Furthermore, the presence of two cations, Cu and Zn, had an inhibitory effect on the removal of Cd ions. In addition, analysis of the zeta potential revealed the flocculation of polyacrylamide-glutathione. The flocculation mechanism of glutathione is mainly chelation, adsorption bridging, and netting sweeping.

Kinetics and mechanistic aspects of removal of heavy metal through gas-liquid sulfide precipitation: A computational and experimental study.

The production of fine particles from extremely high supersaturation has challenged the application of sulfide precipitation in treating heavy metal wastewater due to the difficulty of solid-liquid separation. To this end, a gas-liquid sulfide precipitation reactor for the removal of Cu2+ was designed by controlling the mass transfer and supersaturation levels during sulfidation processes. Particularly, a computational fluid dynamics (CFD) model of the reactor, integrating sulfidation reaction kinetics with two-phase flow hydrodynamics, was first built, followed by examining the effects of H2S(g) bubble diameter and flow rate. Based on the CFD simulation, the rate-limiting step of the gas-liquid sulfide precipitation reaction is the gas-liquid mass transfer process. Either reducing H2S(g) bubble diameter or increasing H2S(g) flow rate can result in the control of reaction rate and supersaturation level in the system. In order to validate the CFD simulations, we measured Cu2+ concentrations during the sulfidation process with the batch experiments. The agreement between computational and experimental results indicated that our mechanistic model can provide a protocol for the design and optimization of the reaction system, allowing one to visualize the time-dependent reaction process and evaluate the performance of a reactor.

Long-term domestication to Mn stresses alleviates the inhibition on anammox process.

Heavy metals such as Mn2+ are common contaminants in ammonium-rich wastewater. The information of Mn2+ effect on anammox process needs further investigation. The short- and long-term effects of Mn2+ on anammox were explored by anammox granular sludge. Batch tests showed that the half inhibition value (IC50 ) of Mn2+ was 4.83 mg/L. The anammox activity was severely inhibited in 0.5 hr under 15 mg/L Mn2+ . However, after long-term domestication by increasing the concentration of Mn2+ , both the low-load reactor (R1) and the high-load reactor (R2) performed well, achieving volumetric nitrogen removal rate of 6.36 kg/(m3 ·d) and 13.99 kg/(m3 ·d), respectively. The average ammonium and nitrite removal efficiency of both reactors under 200 mg/L Mn still maintained above 90%. The results from long-term reactors' operation showed that the serious inhibition effect indicated by the batch test was significantly exaggerated. The granules became dispersed after long-term operation in the high-load reactor (R2) which might be correlated to the high osmotic pressure caused by high Mn2+ load, and the mechanism needs to be investigated further. PRACTITIONER POINTS: The half inhibition value of Mn2+ on anammox sludge was 4.83 mg/L in batch experiment. 200 mg/L Mn2+ did not cause any inhibition on anammox process during long-term operation. Granular sludge is finer under high nitrogen loads with 200 mg/L Mn stress.

Experimental and theoretical insight into hydroxyl and sulfate radicals-mediated degradation of carbamazepine.

Carbamazepine (CBZ), a widely detected pharmaceutical in wastewaters, cannot currently be treated by conventional activated sludge technologies, as it is highly resistant to biodegradation. In this study, the degradation kinetics and reaction mechanisms of CBZ by hydroxyl radical (OH) and sulfate radical ()-based advanced oxidation processes (AOPs) were investigated with a combined experimental/theoretical approach. We first measured the UV absorption spectrum of CBZ and compared it to the theoretical spectrum. The agreement of two spectra reveals an extended π-conjugation system on CBZ molecular structure. The second-order rate constants of OH and with CBZ, measured by competition kinetics method, were (4.63 ±â€¯0.01) × 109 M-1 s-1 and (8.27 ±â€¯0.01) × 108 M-1 s-1, respectively at pH 3. The energetics of the initial steps of CBZ reaction with OH and were also calculated by density functional theory (DFT) at SMD/M05-2X/6-311++G**//M05-2X/6-31 + G**level. Our results reveal that radical addition is the dominant pathway for both OH and . Further, compared to the positive ΔGR0 value for the single electron transfer (SET) reaction pathway between CBZ and OH, the ΔGR0 value for SET reaction between CBZ and is negative, showing that this reaction route is thermodynamically favorable. Our results demonstrated the remarkable advantages of AOPs for the removal of refractory organic contaminants during wastewater treatment processes. The elucidation of the pathways for the reaction of OH and with CBZ are beneficial to predict byproducts formation and assess associated ecotoxicity, providing an evaluation mean for the feasibility of AOPs application.

Design and analysis of continuous-flow reactors for copper sulfide precipitation process by a computational method.

Sulfide precipitation method has been widely applied in heavy metal-polluted wastewater treatment, due to the low solubility of most metal sulfide precipitates. Nevertheless, the relevant hydrodynamics studies on the metal sulfide precipitation process are rarely found in the literature. In this study, three continuous-flow sulfide precipitation reactors (CFSPRs) were designed and evaluated by a computational method. To characterize the process efficiency of copper sulfide precipitation in different reactors, fluid velocity field, species concentration distribution, and reaction rate distribution maps were acquired as simulation results. A two-factor designed set of boundary conditions was used to determine their effects on processing efficiency. The model results indicate that the inflow rate and reactor layout have significant effects on the copper sulfide precipitation process. The layout of reactor no. 3 and the inflow rate of 0.75 m/s prove to have higher treatment efficiencies than those at other conditions. Possible explanations for the simulation results were proposed. The model data of effluent concentration were compared and statistically analyzed with the measured concentrations of copper ion and sulfur ion in the outlet stream, and the results demonstrate a strong correlation between them, which suggests the model is reasonably accurate.

Design and analysis of a novel furnace throat for removing dust particles in flue gas emitted from copper smelting furnace by a computational method.

A novel furnace throat structure was designed to reduce dust particle concentration in the flue gas emitted from the copper smelting industry. A two-stage turbulence model of the furnace throat based on the RNG k-ε model combined with the stochastic trajectory model was developed to analyze the gas flow and particle trajectories in this furnace throat structure. The resulting turbulent flow fields and particle trajectories under different operating conditions were shown and discussed. It indicates that the furnace throat plays an important role in separating the dust particles from the flue gas by applying centrifugal force and subsequent resistance force. Moreover, the effects of the radius of the inner flue, the number of the spiral plate, and the number of the spiral plate turns on the particle collection efficiency were analyzed to optimize the throat structure. The simulation results show that the furnace throat with inner flue radius of 0.05 m, two spiral plates, and two spiral plate turns has the highest particle collection efficiency. Furthermore, a series of experimental tests were conducted to validate the accuracy of the simulation results, and the measured experimental data show a good correlation with the numerical results.

Electrophilicity index as a critical indicator for the biodegradation of the pharmaceuticals in aerobic activated sludge processes.

Improving biodegradation of pharmaceuticals during wastewater treatment is critical to control the release of emerging micropollutants to natural waters. In this study, biodegradation of six model pharmaceuticals was investigated at different initial concentrations in two discrete activated sludge systems, and moreover, the correlation was explored between the biodegradation rate and key molecular properties of the contaminants. First, the biodegradation rates of the pharmaceuticals were measured fitting a pseudo first-order kinetic model to the experimental kinetic data. The degradation rate constants (kbio) were found to negatively correlate to the initial concentration of the chemicals, indicating an inhibitory effect on the microorganisms by the pharmaceuticals. Further examinations of the rate data against the key molecular properties of the pharmaceuticals revealed, for the first time, that the electrophilicity index (ω), a measure of electrophilic power, served as a better indicator of the biodegradability and predictive parameter for the kbio than the conventional log KOW (a measure of hydrophobicity) in the two discrete aerobic activated sludge systems. However, the correlation strength (goodness‒of‒fit) between ω and kbio deteriorated when the reactor turned from aerobic to anoxic and anaerobic conditions, suggesting that electron transfer from pharmaceutical molecules to enzymes was inhibited when dissolved oxygen was deficit or absent. Our results show that ω can potentially serve as a straightforward and robust indicator for predicting the biodegradability of pharmaceutical in conventional activated sludge processes.

Effect of scrubbing by NaClO backwashing on membrane fouling in anammox MBR.

NaClO based chemically enhanced backwash (CEB) is often administered to maintain membrane permeability during the operation of MBR. However, the effect and working mechanism of NaClO concentrations in CEB were rarely investigated. The current investigation examined the changes in membrane resistance, permeate production and membrane morphology with or without CEB in an anammox MBR to reveal the scrubbing effect of different NaClO concentrations (0-596 mg/L). Good cleaning effect indicated by membrane fouling rate of 1.98-2.26 kPa/day and membrane permeate production of 80-88 L was observed when NaClO concentration of 149-596 mg/L was used. The best cleaning effect was observed when 298 mg/L of NaClO was used. To explore the mechanism of CEB action, backwashing foulants were also analyzed. Insoluble EPS transformed into soluble forms like S-EPS or SMP after the sludge was exposed to NaClO. The NaClO based CEB removed 112-675 mg of polysaccharide (PS)/m2 in foulants at NaClO concentration of 149-596 mg/L, which was significantly higher than the value obtained by pure water (35 mg PS/m2). The possible mechanisms behind the detachment of soluble PS seemed as oxidation and sterilization by NaClO. The current investigation provides useful guidelines on NaClO concentrations applied during CEB for anammox MBR.