The Unique CO Activation Effects for Boosting NH3 Selective Catalytic Oxidation over CuOx-CeO2.

Slip NH3 is a priority pollutant of concern to be removed in various flue gases with NOx and CO after denitrification using NH3-SCR or NH3-SNCR, and the simultaneous catalytic removal of NH3 and CO has become one of the new topics in the deep treatment of such flue gases. Synergistic catalytic oxidation of CO and NH3 appears to be a promising method but still has many challenges. Due to the competition for active oxidizing species, CO was supposed to hinder the NH3 selective catalytic oxidation (NH3-SCO). However, it is first found that CO could significantly promote NH3-SCO over the CuOx-CeO2 catalyst. The NH3 conversion rates increased linearly with CO concentrations in the range of 180-300 °C. Specifically, it accelerated by 2.8 times with 10,000 ppm CO inflow at 220 °C. Mechanism studies found that the Cu-O-Ce solid solution was more active for CO oxidation, while the CuOx species facilitated the NH3 dehydrogenation and mitigated the competition of NH3 and CO, further stabilizing the promotion effects. Gaseous CO boosted the generation of active isolated oxygen atoms (Oi) by actuating the Cu+/Cu2+ redox cycle. The enriched Oi facilitated oxidation of NH3 to NO and was conducive to the NH3-SCO via the i-SCR approach. This study tapped the potential of CO for promoting simultaneous catalytic oxidation of coexisting pollutants in the flue gas.

Surface protection method for the magnetic core using covalent organic framework shells and its application in As(III) depth removal from acid wastewater.

Fe3O4-based materials are widely used for magnetic separation from wastewater. However, they often suffer from Fe-leaching behavior under acidic conditions, decreasing their activity and limiting sustainable practical applications. In this study, covalent organic frameworks (COFs) were used as the shell to protect the Fe3O4 core, and the Fe3O4@COF core-shell composites were synthesized for As(III) removal from acid wastewater. The imine-linked COFs can in situ grow on the surface of the Fe3O4 core layer by layer with [COFs/Fe3O4]mol ratio of up to 2:1. The Fe-leaching behavior was weakened over a wide pH range of 1-13. Moreover, such composites keep their magnetic characteristic, making them favorable for nanomaterial separation. As(III) batch adsorption experiments results indicated that, when COFs are used as the shell for the Fe3O4 core, a balance between As(III) removal efficiencies and the thickness of the COF shell exists. Higher As(III) removal efficiencies are obtained when the [COFs/Fe3O4]mol ratios were < 1.5:1, but thicker COF shells were not beneficial for As(III) removal. Such composites also exhibited better As(III) removal performances in the pH range of 1-7. Over a wide pH range, the zeta potential of Fe3O4@COF core-shell composites becomes more positive, which benefits the capture of negative arsenic ions. In addition, thinner surface COFs were favorable for mass transfer and facilitating the reaction of Fe and As elements. Our study highlights the promise of using COFs in nanomaterial surface protection and achieving As(III) depth removal under acidic conditions.

Production of H2S with a Novel Short-Process for the Removal of Heavy Metals in Acidic Effluents from Smelting Flue-Gas Scrubbing Systems.

Direct sulfidation using a high concentration of H2S (HC-H2S) has shown potential for heavy metals removal in various acidic effluents. However, the lack of a smooth method for producing HC-H2S is a critical challenge. Herein, a novel short-process hydrolysis method was developed for the on-site production of HC-H2S. Near-perfect 100% efficiency and selectivity were obtained via CS2 hydrolysis over the ZrO2-based catalyst. Meanwhile, no apparent residual sulfur/sulfate poisoning was detected, which guaranteed long-term operation. The coexistence of CO2 in the products had a negligible effect on the complete hydrolysis of CS2. H2S production followed a sequential hydrolysis pathway, with the reactions for CS2 adsorption and dissociation being the rate-determining steps. The energy balance indicated that HC-H2S production was a mildly exothermic reaction, and the heat energy could be maintained at self-balance with approximately 80% heat recovery. The batch sulfidation efficiencies for As(III), Hg(II), Pb(II), and Cd(II) removal were over 99.9%, following the solubilities (Ksp) of the corresponding metal sulfides. CO2 in the mixed gas produced by CS2 hydrolysis did not affect heavy metals sulfidation due to the presence of abundant H+. Finally, a pilot-scale experiment successfully demonstrated the practical effects. Therefore, this novel on-site HC-H2S production method adequately achieved heavy metals removal requirements in acidic effluents.

Multi-roles of SO2 to enhance the removal of arsenic from wastewater in sulfidation processes.

Sulfidation has been an efficient method for arsenic (As) removal from acid wastewater, yet it is inefficient under neutral and weak acid conditions. The higher pH values resulted in the formation of the unstable As-S precipitates, especially employing Na2S as the vulcanizing agent as it can increase the pH value dramatically. Here, we found that SO2 exhibited excellent multi-roles in As removal when applying H2S-sulfidation method. The acidification effect of SO2 lead to the decreasing of pH values, guaranteed the stable As-S precipitates formation. Through the SO2 pre-treatment method, the results indicated that the pH values decreased from 7 to 2.8, with the increased H2S utilization efficiencies for As(III) removal from 20.9% to 92.0%. Moreover, SO2 post-treatment not only increased the As(III) removal efficiency, but also eliminated the excessive sulfides in solution. The reaction mechanism analysis indicated that the liquid comproportionation reaction between SO2 and excessive sulfides plays a vital role. The generated nascent sulfur (N-S0) can adsorb arsenic species and promote the agglomeration of As(III)-S precipitates. Furthermore, the SO2 and H2S co-treatment exhibited excellent As(V) removal performance. This study provides a new alternative method to improve the H2S-sulfidation process with SO2 for As removal from wastewater.

Dual-functional Sites for Selective Adsorption of Mercury and Arsenic ions in [SnS4]4-/MgFe-LDH from Wastewater.

Heavy metals existed as multiple types in wastewater, enhanced the difficulty for disposal, and aroused huge environmental issues. High selective adsorption of the most hazardous heavy metals is one important method for water purification and resource utilization. In this study, we assembled the [SnS4]4- clusters and MgFe-based layered double hydroxide (LDH) to synthesize the [SnS4]4-/LDH composites, to capture mercury and arsenic ions simultaneously. The results indicated that such composite exhibited excellent mercury and arsenic removal performance with higher than 99% removal efficiency at a wide pH range. The uptake of mercury was ascribed to the [SnS4]4- clusters sites while the arsenic removal was mainly due to the existence of Fe site in LDH composite. The inserted [SnS4]4- clusters can enlarge the surface areas and create a hierarchical pore channel due to the increased interlayer spacing of LDH, which can enhance the adsorption capacity. The different adsorption mechanisms were also indicated by dynamic analysis. Pseudo-second-order kinetic model was more suitable for both Hg(II) and As(III) adsorption in the dual-heavy metal solution, and neither Langmuir isotherm model nor Freundlich isotherm model fitted the Hg(II) and As(III) adsorption in the mixed solution. The adsorption progress was influenced due to the coexistence of another heavy metal. Besides, mercury can be collected from the spent materials using a thermal-heating method. Such composite exhibits promising potential for mercury recycling.