π-π Stacking at the Perovskite/C60 Interface Enables High-Efficiency Wide-Bandgap Perovskite Solar Cells.

Interface passivation is a key method for improving the efficiency of perovskite solar cells, and 2D/3D perovskite heterojunction is the mainstream passivation strategy. However, the passivation layer also produces a new interface between 2D perovskite and fullerene (C60), and the properties of this interface have received little attention before. Here, the underlying properties of the 2D perovskite/C60 interface by taking the 2D TEA2PbX4 (TEA = C6H10NS; X = I, Br, Cl) passivator as an example are systematically expounded. It is found that the 2D perovskite preferentially exhibits (002) orientation with the outermost surface featuring an oriented arrangement of TEACl, where the thiophene groups face outward. The outward thiophene groups further form a strong π-π stacking system with C60 molecule, strengthening the interaction force with C60 and facilitating the creation of a superior interface. Based on the vacuum-assisted blade coating, wide-bandgap (WBG, 1.77 eV) perovskite solar cells achieved impressive records of 19.28% (0.09 cm2) and 18.08% (1.0 cm2) inefficiency, respectively. This research not only provides a new understanding of interface processing for future perovskite solar cells but also lays a solid foundation for realizing efficient large-area devices.

Flexible electronics for heavy metal ion detection in water: a comprehensive review.

Flexible electronics offer a versatile, rapid, cost-effective and portable solution to monitor water contamination, which poses serious threat to the environment and human health. This review paper presents a comprehensive exploration of the versatile platforms of flexible electronics in the context of heavy metal ion detection in water systems. The review overviews of the fundamental principles of heavy metal ion detection, surveys the state-of-the-art materials and fabrication techniques for flexible sensors, analyses key performance metrics and limitations, and discusses future opportunities and challenges. By highlighting recent advances in nanomaterials, polymers, wireless integration, and sustainability, this review aims to serve as an essential resource for researchers, engineers, and policy makers seeking to address the critical challenge of heavy metal contamination in water resources. The versatile promise of flexible electronics is thoroughly elucidated to inspire continued innovation in this emerging technology arena.

Smart Wrinkled Interfaces: Patterning, Morphing, and Coding of Polymer Surfaces by Dynamic Anisotropic Wrinkling.

In contrast to traditional static surfaces, smart patterned surfaces with periodical and reversible morphologies offer limitless opportunities for encoding surface functions and properties on demand, facilitating their widespread application as functional building blocks in various devices. Advances in intelligently controlling the macroscopic properties of these smart surfaces have been accomplished through various techniques (such as three-dimensional printing, imprint lithography and femtosecond laser) and responsive materials. In contrast to the sophisticated techniques above, dynamic anisotropic wrinkling, taking advantage of dynamic programmable manipulation of surface wrinkling and its orientation, offers a powerful alternative for fabricating dynamic periodical patterns due to its spontaneous formation, versatility, convenient scale-up fabrication, and sensitivity to various stimuli. This review comprehensively summarizes recent advances in smart patterned surfaces with dynamic oriented wrinkles, covering design principles, fabrication techniques, representative types of physical and chemical stimuli, as well as fine-tuning of wrinkle dimensions and orientation. Finally, advanced applications of these smart patterned surfaces are presented, along with a discussion of current challenges and future prospects in this rapidly evolving field. This review would offer some insights and guidelines for designing and engineering novel stimuli-responsive smart wrinkled surfaces, thereby facilitating their sustainable development and progressing toward commercialization.

Effects of potassium-mediated electrical communication inhibition on nitrogen removal in microbial fuel cells.

Potassium ion signaling mediates microbial communication in electroactive biofilms within microbial fuel cells (MFCs), but its role in nitrogen removal remains unclear. This study investigated the impact of inhibiting potassium signaling on nitrogen removal in MFCs using tetraethylammonium chloride (TEA) as an inhibitor. Results demonstrated that 5 mM and 10 mM TEA reduced the maximum power generation of MFCs from 77.95 mW/cm2 to 57.18 mW/cm2 and 48.23 mW/cm2, respectively. Correspondingly, total nitrogen (TN) removal efficiency was decreased from 46.57 ± 1.01% to 35.93 ± 0.63% and 38.97 ± 0.74%, respectively. This decline was attributed to inhibited potassium ion signaling, which compromised the electrochemical performance of the MFC and hindered the nitrogen removal process. The relative abundance of exoelectrogen Geobactor decreased from 15.37% to 5.17% and 8.05%, while the relative abundance of cathodic nitrifying bacteria Nitrosomonas decreased from 17.87% to 4.92% and 3.63% under 5 mM and 10 mM TEA. These findings underscore the crucial role of potassium ion signaling in enhancing the bioelectrochemical nitrogen removal process in MFCs.

Pretreatment of sludge with sodium iron chlorophyllin-H2O2 for enhanced biogas production during anaerobic digestion.

This study investigated a novel sodium iron chlorophyllin-H2O2 (SIC-H2O2) sludge pretreatment strategy before anaerobic digestion to enhance methane production. The efficiencies and mechanism of the proposed strategy to enhance sludge biodegradability were explored. The SIC-H2O2 pretreatment could enhance the oxidation performance for sludge floc disintegration to dissociate TB-EPS into S-EPS increased SCOD to 521.38 mg/L. The increase of solubilization and release of EPS with the pretreatment facilitate the biogas production at 702 L kg-1 VS, which was 3-folds of the control and significantly higher than other pretreatments. The result of excitation-emission matrix and parallel factor (EEM-PARAFAC) analysis showed that the SIC-H2O2 pretreatment enhanced the dissociation of TB-EPS fractions, especially the protein-like and soluble microbial by-product-like substances. Electron paramagnetic resonance (EPR) results provided evidence for homolytic catalysis H2O2 for the generation OH and the production of high-valent (Por)FeIV(O) intermediates. Synergistic effects of reactive oxygen species (OH, H2O2 and /HO2) and (Por)FeIV(O) enhanced the EPS disintegration during SIC-H2O2 pretreatment. The mixed-acid type fermentation provided continuous VFAs supply under the enrichment of Chloroflexi and Actinobacteria and multiplication Methanosaeta also promoted methane production. This research provides a feasible pretreatment strategy increase sludge biodegradability and enhance biogas production in the anaerobic digestion process.

Deciphering the role of microplastic size on anaerobic sludge digestion: Changes of dissolved organic matter, leaching compounds and microbial community.

Here the role of microplastic size on dissolved organic matter, leaching compounds and microbial community during anaerobic sludge digestion was evaluated. Compared to that without the addition of polyvinyl chloride (PVC), during the 30 days' incubation, the anaerobic sludge digestion by adding PVC at the size of 75 µm and the concentration of 2.4 g/g volatile solids (VS) showed a 8.5% lower cumulative methane production, while a 17.9% higher cumulative methane production was noted by adding PVC at the size of 3000 µm and the concentration of 2.4 g/g VS. A long-term fed-batch laboratory-scale fermenter test for 147 days further testified, that higher removal efficiencies of total solids, volatile solids, and total chemical oxygen demand, and higher methane production were noted by adding PVC (2.4 g/g VS, 3000 µm) into the fermenter. More interestingly, higher concentrations of proteins, polysaccharides, volatile fatty acids, and soluble microbial by-products component were noted in the liquid phase of sludge drawn from the fermenter added with PVC since the biomass therein showed higher efficiencies of solubilization, hydrolysis, acidification, and methanogenesis. Moreover, as identified from the fermenter added with PVC, dibutyl phthalate (DBP) was the most predominant leaching phthalates compound, although the biomass therein showed a 93.4% anaerobic biodegradability of DBP. The leaching of DBP drove the predominance of microbial community towards Synergistota and Methanosaeta. More irregular elliptical shallow dimples were noted on the PVC surface after 147 days' incubation, accompanied with abundances of Proteobacteria, Actinobacteriota, Chloroflexi, Methanosaeta and Methanobacterium. The results from this study showed that the size of microplastic was a crucial factor in evaluating its impact on anaerobic sludge digestion.

Recirculation of reject water in deep-dewatering process to influent of wastewater treatment plant and dewaterability of sludge conditioned with Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8: From bench to pilot-scale study.

Deep dewatering of sewage sludge pretreated with advanced oxidation processes (AOPs) is a strategy for efficient sludge reduction and subsequent disposal. The pretreatment and dewatering performance of sludge conditioned with three types of AOPs (Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8), compared with sludge conditioned with traditional conditioner (Fe3+/CaO), were investigated in both bench and pilot-scale tests. All of those conditioner systems could reduce the water content of dewatered sludge cake to below 60 wt% in bench-scale (about 16 kg raw sludge per round) and pilot-scale (approximate 800 kg raw sludge per round) diaphragm filter press dewatering. Compared with raw sludge, the deep-dewatering filtrate after different conditioning and dewatering processes had higher ammonia nitrogen (NH4+-N) and chemical oxygen demand (COD) contents due to the degradation of organic matter, and much lower total phosphorus (TP) content due to the formation of iron phosphate precipitate. A better biodegradability (i.e. higher BOD5/COD ratio) was found in the deep-dewatering filtrate of sludge conditioned with Fe2+/H2O2 (25.2 %) and Fe2+/Ca(ClO)2 (17.4 %). Most of the heavy metals (Cr, Cu, Ni, and Pb) (>79 wt%) have remained in the dewatered sludge cake, and most of the Cl element (>90 wt%) in the sludge pretreated by Fe2+/Ca(ClO)2 and Fe3+/CaO was kept in the filtrate, rather than the dewatered sludge cake. Based on the pilot-scale experimental results, if all the filtrate in the deep-dewatering process returned to the influent of WWTP, the loading ratios of TP, NH4+-N, COD in the four conditioner systems were less than 3 wt%. The above results proved that the AOPs conditioned sludge could achieve deep-dewatering in pilot-scale and the direct recirculation of deep-dewatering filtrate to the influent of wastewater treatment plant was feasible.

Enhancing waste activated sludge dewaterability by reducing interaction energy of sludge flocs.

How to efficiently improve waste activated sludge (WAS) dewaterability is a common challenge in WAS treatment and management throughout world. The interaction energy of sludge flocs is of great importance for sludge dewaterability. In this study, the relationship among the repulsive force of sludge flocs, hydrophilic/hydrophobic characteristics of sludge flocs, and sludge dewaterability have been quantitatively and qualitatively investigated based on extended Derjaguin-Landau-Verwey-Overbeek theory for the first time. The energy barrier of sludge flocs has good correlations with sludge dewaterability (p < 0.05). Trivalent cations (Al3+ and Fe3+) and Fenton's reagent reduced the interfacial free energy (ΔG) from 9.4 mJ/m2 of raw sludge to -34.2 (Al3+), -60.5 (Fe3+), and -63.2 (Fenton) mJ/m2, respectively, indicating that the hydrophilic surfaces of the sludge flocs converted to hydrophobic (△G < 0), and decreasing Lewis acid-base interaction energy (WAB) of sludge flocs. In addition, most of the trivalent cations (Al3+ and Fe3+) were attached to sludge flocs, leading to neutralize negative charges and mitigate electrostatic interaction energy (WR) of sludge flocs. The reduction of WAB and WR eliminated energy barrier of sludge flocs and repulsive force between sludge flocs. In comparison, monovalent (Na+ and K+) and bivalent (Ca2+ and Mn2+) cations cannot completely change the hydrophilic surface characteristic and negative charge of sludge flocs. The existed energy barrier prevented sludge flocs to agglomerate with each other, thus resulting in a worse dewaterability. This study illustrated that reducing interaction energy of sludge flocs played a critical role to improve sludge dewaterability.

Stepwise extraction of Fe, Al, Ca, and Zn: A green route to recycle raw electroplating sludge.

Electroplating sludge is a hazardous waste produced in large quantities in the electroplating industry during production. It is rich in heavy metal resources and can be recovered as value-added heavy metal products. To recover Zn in electroplating sludge, Fe/Al/Ca impurities were effectively removed as hematite, boehmite, and calcium sulfate, respectively, via a facile hydrothermal method with reduction of nitric acid by addition of glucose. After the sludge was dissolved in nitric acid, the generated solution contained 6.1 g/L of Zn, 2.2 g/L of Fe, 2.5 g/L of Al, and 2.9 g/L of Ca. First, approximately 100% Fe was extracted as hematite nanoparticles containing 94.6 wt% Fe2O3 after the solution was treated at 190 °C for 6 h. Second, when the temperature was elevated to 270 °C, nearly 99% Al was isolated as boehmite particles containing 95.2 wt% Al2O3. Third, more than 98% Ca was removed as anhydrite, which contained 95.9 wt% CaSO4, by adding sulfuric acid. During the steps, the total loss of Zn was less than 3%, and 5.75 g/L of residual Zn was recovered as zincite containing 92.2 wt% ZnO by adjusting the pH to 8. The dissolved Fe, Al, and Ca impurities were successfully removed as purified hematite, boehmite, and anhydrite, respectively, through the stepwise separation method by adjusting reaction temperatures and pH. The high content of Zn in the electroplating sludge was finally purified as zincite.

Enhanced quorum sensing of anode biofilm for better sensing linearity and recovery capability of microbial fuel cell toxicity sensor.

MFC toxicity sensor has major hindrances that limit its practical application, such as the poor concentration-response relationship and inferior recovery capability after high toxicity shock. Till now, the direct influence of intrinsic properties on the performance of MFC toxicity sensor has not been well understood. Quorum sensing (QS) is a cell-to-cell communication strategy that indirectly affects the intrinsic properties of electroactive biofilms. In this work, commercially available QS autoinducers (AHLs) were applied to MFC toxicity sensor to manipulate anode biofilm for better sensing performance. The results showed that the addition of AHLs (C6-HSL, 3-OXO-C12-HSL) led to higher sensing linearity to a wider range of Pb2+. The voltage of MFC sensors with AHLs addition fully recovered even after 10 mg/L Cu2+ shock, indicating an enhanced recovery capability of MFC toxicity sensor. It was found that higher live/dead cells ratio and increased exoelectrogen Geobacter abundance were responsible for the superior sensing linearity and recovery capability of MFC toxicity sensor. Our work presented a novel and effective way to advance the process of MFC toxicity sensor application from the perspective of EABs.

Improvement of sludge dewaterability by ammonium sulfate and the potential reuse of sludge as nitrogen fertilizer.

A novel method to enhance sludge dewaterability with ammonium sulfate ((NH4)2SO4) was proposed, and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizers was evaluated. Compared with raw sludge, 87.91% reduction of capillary suction time (CST) and 88.02% reduction of specific resistance to filtration (SRF) after adding 80% (m/m) (NH4)2SO4 were achieved, with 38.49% of protein precipitated simultaneously. The (NH4)2SO4 dose destroyed cell membrane, resulting in the release of intracellular water by converting bound water into free water, thus enhancing sludge dewaterability. In the solid phase, the content of protein-N increased, and larger protein aggregates were formed. The (NH4)2SO4 dose destroyed the hydration shell, making proteins to exhibit hydrophobic interactions, and to be aggregated, and precipitated from the liquid phase. When incubated Pennisetum alopecuroides L. with the dewatered sludge cake and filtrate after dewatering and conditioning with (NH4)2SO4, the germination rate of grass seed and shoot lengths both increased while compared with those incubated with dewatered sludge cake and filtrate of the raw sludge. This study might provide insights into sustainable sludge treatment by integrating sludge dewatering and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizer via treatment with (NH4)2SO4.

Performance evaluation of microbial fuel cell for landfill leachate treatment: Research updates and synergistic effects of hybrid systems.

Over half of century, sanitary landfill was and is still the most economical treatment strategy for solid waste disposal, but the environmental risks associated with the leachate have brought attention of scientists for its proper treatment to avoid surface and ground water deterioration. Most of the treatment technologies are energy-negative and cost intensive processes, which are unable to meet current environmental regulations. There are continuous demands of alternatives concomitant with positive energy and high effluent quality. Microbial fuel cells (MFCs) were launched in the last two decades as a potential treatment technology with bioelectricity generation accompanied with simultaneous carbon and nutrient removal. This study reviews capability and mechanisms of carbon, nitrogen and phosphorous removal from landfill leachate through MFC technology, as well as summarizes and discusses the recent advances of standalone and hybrid MFCs performances in landfill leachate (LFL) treatment. Recent improvements and synergetic effect of hybrid MFC technology upon the increasing of power densities, organic and nutrient removal, and future challenges were discussed in details.

Facile and Cost-Effective Approach for Copper Recovery from Waste Printed Circuit Boards via a Sequential Mechanochemical/Leaching/Recrystallization Process.

The recovery of copper (Cu0) from waste printed circuit boards (WPCBs) is a great challenge as a result of its heterogeneous structural properties, with a mixture of metals, epoxy resin, and fiberglass. In this study, a three-step sequential process, including mechanochemical processing, water leaching, and recrystallization, for Cu0 recovery from WPCB powder is reported. Potassium persulfate (K2S2O8), instead of acid/alkali reagents, was employed as the sole reagent in the cupric sulfate (CuSO4) regeneration process. Complete oxidation of Cu0 in the WPCBs to copper oxide (CuO) and CuSO4 was first achieved during mechanochemical processing with K2S2O8 as the solid oxidant, and the K2S2O8 was simultaneously converted to sulfate compounds [K3H(SO4)2] via a solid-solid reaction with epoxy resin (C nH mO y) as the hydrogen donator under mechanical force. The rapid leaching of Cu species in the forms of CuO and CuSO4 was therefore easily realized with pure water as a nontoxic leaching reagent. The kinetics of the leaching process of Cu species was confirmed to follow the shrinking nucleus model controlled by solid-film diffusion. Finally, CuSO4·5H2O was successfully separated by cooling crystallization of the hot saturated solution of sulfate salt [K2Cu(SO4)2·6H2O]. An efficient conversion of Cu0 to CuSO4·5H2O product, for WPCB recycling, was therefore established.

A micromilled microgrid sensor with delaminated MXene-bismuth nanocomposite assembly for simultaneous electrochemical detection of lead(II), cadmium(II) and zinc(II).

A delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite was synthesized for the construction of a microgrid electrochemical sensor via mechanical milling. The Bi@d-Ti3C2 nanocomposite was synthesized by accumulation of Bi(III) on the surface of delaminated Ti3C2 nanosheets through electrostatic attraction and subsequent in-situ growth of bismuth nanorods. Under optimized experimental conditions, the sensor exhibits (a) linear responses to Pb(II), Cd(II) and Zn(II) in the concentration range from 1 to 20 µg L-1, (b) well separated peak potentials at -0.54 V, -0.76 V and - 1.15 V vs. Ag/AgCl, (c) sensitivities of 0.98, 0.84 and 0.60 µA L µg-1, and (d) detection limits of 0.2, 0.4 and 0.5 µg L-1, respectively. This performance is attributed to the uniform dispersion of Bi nanorods on electrically conductive delaminated Ti3C2 MXene, and to the enhanced diffusion due to the microgrid structure. Graphical abstractSchematic representation of a microgrid sensor based on delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite for the simultaneous electrochemical determination of Pb(II), Cd(II) and Zn(II).

Valorization of manganese-containing groundwater treatment sludge by preparing magnetic adsorbent for Cu(II) adsorption.

Mn-containing sludge from groundwater treatment was converted to magnetic particles (MPs) via a one-step hydrothermal method using sodium ascorbate (SA) as the reductant. The MPs were characterized by X-ray diffraction spectroscopy, Mössbauer spectroscopy, X-ray fluorescence spectroscopy, magnetometry and Gran titration and the results showed that magnetic jacobsite was obtained as an intermediate product in transformation of Fe/Mn oxides to siderite and rhodochrosite. When the molar ratio of SA to Mn in the sludge was two, the produced MPs-2 contained a mixture of ferrihdyrite, hematite, jacobsite and Si/Al oxides, and could magnetize at 2.4 emu/g. Ferrihydrite content in MPs decreased with increase of the SA/Mn molar ratio, leading to decrease of the surface sites concentration (Hs). Thus, MPs-2 contained optimized Hs of 6.7 mmoL/g and a desirable adsorption capacity of Cu(II) (73.1 mg/g). The adsorption isotherms of MPs-2 on Cu(II) complied with the Langmuir model and the adsorption kinetics fitted well with the pseudo-second-order model. The major mechanism of adsorption was cationic exchange of the coordinated H and Na ions on MPs-2 surface sites with the Cu(II) ions. This study was the first time to report preparation of MPs by recycling Mn-containing sludge, which could be used as a high-capacity and low-cost adsorbent in treatment of heavy metal-containing wastewater.

A green recycling process of the spent lead paste from discarded lead-acid battery by a hydrometallurgical process.

In this study, a green recycling process of discarded lead-acid battery paste, which could avoid both the smelting and electro-winning route has been developed. Leaching reagents containing sodium citrate, acetic acid and hydrogen peroxide were reacted with spent lead paste in aqueous media at the pH of 5-6. Lead paste was leached and formed into lead citrate precursor, which was recrystallized and separated from the solution. The optimal conditions for the leaching process at room temperature were found to be the: concentration of acetic acid solution of 0.92 mol L-1; concentration of sodium citrate solution of 0.478 mol L-1; initial mass ratio of solid spent lead paste to liquid (solid/liquid ratio) of 1/5 g/mL; and reaction time of 2 hours. The results showed that the desulphurization efficiency of lead paste was up to 99.9%. The optimal conditions for lead citrate re-crystallization from the leaching mixed solution were found to be the re-crystallization temperature of 55oC for 5 hours in a water bath. The lead citrate precursor synthesized from discarded lead-acid battery pastes was the chemical formula of Pb3(C6H5O7)2·3H2O with columnar shape in the length of 30-50 µm, which was easily separated from the leaching solution. The results of kilogram-scale experiments made progress easier for obtaining the ultrafine lead oxide product (PbO and Pb) from discarded lead-acid battery paste.

Stabilization and Mineralization Mechanism of Cd with Cu-Loaded Attapulgite Stabilizer Assisted with Microwave Irradiation.

Cadmium (Cd) in soil was stabilized using copper loaded attapulgite (Cu/ATP) in a microwave (MW) system. Excellent Cd stability in soil was achieved with Cu/ATP addition due to higher adsorption energy (1.38 eV) of Cu/ATP for Cd than that of ATP (∼1 eV), confirmed by density functional theory calculations. The strong hybridization of the s, p-orbitals of Cd with the s, p, d-orbitals of Cu on ATP contributed to the strong interactions between Cd and Cu/ATP. The stability performance of Cd in Cu/ATP-treated soil was further enhanced after MW irradiation through a series of phase transformation to more stable Cd-bearing crystalline minerals. The transformation was initiated by MW-induced "hot spots", which created cationic vacancy on Cu/ATP surface and enhanced the solid-state reactions between Cd and Cu/ATP framework. The total bond orders of Cd in the formed CdAl4O7 crystalline mineral elevated to 3.38, which was 5-fold higher than that for Cd on Cu/ATP, ensuring the long-term stability of Cd even after 360 curing days. Cd contaminated soil from a former industrial electroplating site was successfully stabilized with the proposed strategy. The research provides an effective stabilization strategy as well as a comprehensive understanding of the mechanism of long-term Cd stabilization.

Visible Light Driven Organic Pollutants Degradation with Hydrothermally Carbonized Sewage Sludge and Oxalate Via Molecular Oxygen Activation.

Converting sewage sludge into functional environmental materials has become an attractive sewage sludge disposal route. In this study, we synthesize a sewage sludge-based material via a facile one-pot hydrothermal carbonization method and construct a visible light molecular oxygen activation system with hydrothermally carbonized sewage sludge (HTC-S) and oxalate to degrade various organic pollutants. It was found that iron species of HTC-S could chelate with oxalate to generate H2O2 via molecular oxygen activation under visible light, and also promote the H2O2 decomposition to produce •OH for the fast organic pollutants degradation. Taking sulfadimidine as the example, the apparent degradation rate of HTC-S/oxalate system was almost 5-20 times that of iron oxides/oxalate system. This outstanding degradation performance was attributed to the presence of iron-containing clay minerals in HTC-S, as confirmed by X-ray diffraction measurements and Mössbauer spectrometry. In the oxalate solution, these iron-containing clay minerals could be excited more easily than common iron oxides under visible light, because the silicon species strongly interacted with iron species in HTC-S to form Fe-O-Si bond, which lowered the excitation energy of Fe-oxalate complex. This work provides an alternative sewage sludge conversion pathway and also sheds light on the environmental remediation applications of sewage sludge-based materials.

An Emission-Free Vacuum Chlorinating Process for Simultaneous Sulfur Fixation and Lead Recovery from Spent Lead-Acid Batteries.

Spent lead-acid battery recycling by using conventional technologies is usually accompanied by releases of lead-containing wastewater as well as emissions of sulfur oxides and lead particulates that may potentially cause secondary pollution. This study developed a vacuum chlorinating process for simultaneous sulfur fixation and high-purity lead chloride (PbCl2) recovery from spent lead paste by using calcium chloride (CaCl2) and silicon dioxide (SiO2) as reagents. The process train includes pretreatment, simultaneous PbCl2 production and sulfur fixation, and PbCl2 volatilization. The pretreatment eliminated chlorine emission from direct chlorinating reaction of PbO2 in the initial S-paste (PbSO4/PbO2/PbO/Pb). During the subsequent PbCl2 production and sulfur fixation step, lead compounds in the P-paste (PbSO4/PbO) was converted to volatile PbCl2, and sulfur was simultaneously fixed to the solid residues in the form of CaSO4 to eliminate the emission of sulfur oxides. The final step, PbCl2 volatilization under vacuum, is a physical phase-transformation process of ionic crystals, following a zeroth-order kinetic model. A cost estimate indicates a profit of USD $ 8.50/kg PbCl2. This process offers a novel green lead recovery alternative for spent lead-acid batteries with environmental and economic benefits.

Simulation on flow field and gas hold-up of a pilot-scale oxidation ditch by using liquid-gas CFD model.

A liquid-gas two-phase computational fluid dynamics (CFD) model was developed to simulate flow field and gas hold-up in a pilot-scale oxidation ditch (OD). The volume of fluid (VOF) model and the mass flow inlet boundary condition for gas injection were introduced in this model. The simulated values of the flow velocities and the gas hold-up were verified by experimental measurements in the pilot-scale OD. The results showed that the gas hold-up at test-site 3, immediately downstream of the surface aerator, was the highest among all three test-sites. Most of the gas existed in the upper portion of the ditch and was close to the inner side of the channel. Based on the liquid-gas two-phase CFD model, three operating conditions with different setting height ratios of the submerged impellers were simulated. The simulated results suggested that the setting heights of the submerged impellers have significant impacts on the flow velocity distribution. Lowering the setting height could increase the flow velocity in the pilot-scale OD. An optimal setting height ratio of 0.273 was proposed, which would be beneficial for minimizing sludge sedimentation, especially near the inner side of the curve bend.