Electrochemical Reduction of Flue Gas Denitrification Wastewater to Ammonia Using a Dual-Defective Cu2O@Cu Heterojunction Electrode.

Wet flue gas denitrification offers a new route to convert industrial nitrogen oxides (NOx) into highly concentrated nitrate wastewater, from which the nitrogen resource can be recovered to ammonia (NH3) via electrochemical nitrate reduction reactions (NITRRs). Low-cost, scalable, and efficient cathodic materials need to be developed to enhance the NH3 production rate. Here, in situ electrodeposition was adopted to fabricate a foamy Cu-based heterojunction electrode containing both Cu-defects and oxygen vacancy loaded Cu2O (OVs-Cu2O), which achieved an NH3 yield rate of 3.59 mmol h-1 cm-2, NH3 Faradaic efficiency of 99.5%, and NH3 selectivity of 100%. Characterizations and theoretical calculations unveiled that the Cu-defects and OVs-Cu2O heterojunction boosted the H* yield, suppressed the hydrogen evolution reaction (HER), and served as dual reaction sites to coherently match the tandem reactions kinetics of NO3-to-NO2 and NO2-to-NH3. An integrated system was further built to combine wet flue gas denitrification and desulfurization, simultaneously converting NO and SO2 to produce the (NH4)2SO4 fertilizer. This study offers new insights into the application of low-cost Cu-based cathode for electrochemically driven wet denitrification wastewater valorization.

Multimedia Mercury Recovery from Coal-Fired Power Plants Utilizing N-Containing Conjugated Polymer Functionalized Fly Ash.

To recover multimedia mercury from coal-fired power plants, a novel N-containing conjugated polymer (polyaniline and polypyrrole) functionalized fly ash was prepared, which could continuously adsorb 99.2% of gaseous Hg0 at a high space velocity of 368,500 h-1 and nearly 100% of aqueous Hg2+ in the solution pH range of 2-12. The adsorption capacities of Hg0 and Hg2+ reach 1.62 and 101.36 mg/g, respectively. Such a kind of adsorbent has good environmental applicability, i.e. good resistance to coexisting O2/NO/SO2 and coexisting Na+/K+/Ca2+/Mg2+/SO42-. This adsorbent has very low specific resistances (6 × 106-5 × 109 Ω·cm) and thus can be easily collected by an electrostatic precipitator under low-voltage (0.1-0.8 kV). The Hg-saturated adsorbent can desorb almost 100% Hg under relatively low temperature (<250 °C). Characterization and theoretical calculations reveal that conjugated-N is the critical site for adsorbing both Hg0 and Hg2+ as well as activating chlorine. Gaseous Hg0 is oxidized and adsorbed in the form of HgXClX(ad), while aqueous Hg2+ is adsorbed to form a complex with conjugated-N, and parts of Hg2+ are reduced to Hg+ by conjugated-N. This adsorbent can be easily large-scale manufactured; thus, this novel solid waste functionalization method is promising to be applied in coal-fired power plants and other Hg-involving industrial scenes.

A critical review on the technique and mechanism of microwave-based denitrification in flue gas.

Microwave radiation has received extensive attention due to its significant thermal and non-thermal effects, and the development of MW-based denitrification in flue gas has become one of the most promising methods to avoid the defects of ammonia escape, high temperature and cost in traditional SCR. This review introduces the thermal and non-thermal effects of microwaves and divides MW-based denitrification methods into MW reduction and oxidation denitrification, systematically summarizes these denitrification methods, including MW discharge reduction, MW-induced catalytic reduction using active carbon, molecular sieves, metal oxides (transition metals, perovskites, etc.), MW-induced oxidation denitrification with and without additional oxidant, and discusses their removal pathway and mechanism. Finally, several research prospects and directions regarding the development of microwave-based denitrification methods are provided.

Removal and Recovery of Gaseous Elemental Mercury Using a Cl-Doped Protonated Polypyrrole@MWCNTs Composite Membrane.

Due to the restrictions on mercury mining, recovering the mercury from mercury-containing waste is attracting increasing attention. This study successfully achieved the removal and recovery of gaseous elemental mercury (Hg0) by using membrane technology. A novel composite membrane of Cl-doped protonated polypyrrole-coated multiwall carbon nanotubes (Cl-PPy@MWCNTs) was fabricated in which MWCNTs acted as the framework to support the active component Cl-PPy. The morphology, structure, and composition of the prepared membranes were determined by field emission scanning electron microcopy, energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, etc. The composite membrane exhibited an excellent performance in Hg0 removal (97.3%) at a high space velocity of 200,000 h-1. The dynamical adsorption capacity of Hg0 was 3.87 mg/g when the Hg0 breakthrough reached 10%. The adsorbed Hg0 could be recovered/enriched via a leaching process using acidic NaCl solution; meanwhile, the membrane was regenerated. The recovered mercury was identified in the form of Hg2+, with a recovery efficiency of over 99%. Density functional theory calculations and mechanism analysis clarified that the electrons of Hg0 transported to the delocalized electron orbits of protonated PPy and then combined with Cl- to form Hg2Cl2/HgCl2. Finally, we first demonstrated that the analogous protonated conductive polymers (e.g., polyaniline) also possessed good Hg0 removal ability, implying that such species may offer more outstanding answers and attract attention in future.

Simultaneous removal of SO2, NO and Hg0 using an enhanced gas phase UV-AOP method.

The core for simultaneous removal of SO2, NO and Hg0 is the oxidation of NO and Hg0. Radical induced oxidation of NO and Hg0 is considered to be the most efficient method. We develop a novel gas phase advanced oxidation process (AOP) of UV-Heat/H2O2-NaClO2 to simultaneously remove SO2, NO and Hg0 due to a great synergism between H2O2 and NaClO2 under thermal and ultraviolet (UV) co-catalysis. The results indicated that the SO2 removal was always good, while the removal of NO and Hg0 was affected by NaClO2 and UV. Higher catalytic temperature and longer flue gas residence time favored the removal of NO and Hg0. The presence of SO2 and NO facilitated Hg0 removal. Kinetics analyses were conducted to provide the reaction rate of removal of NO and Hg0 under different conditions. X-ray photoelectron spectroscopy (XPS) revealed the product composition as Cl-, Hg2+, NO3- and SO42-. Electron spin resonance (ESR) tests confirmed the generation of HO. Cost analyses demonstrated the better cost performance of the proposed method compared to SCR-ACI combined method. HO and ClO2 were proved to be the main oxidant. The reaction mechanism for removal of NO and Hg0 by using UV-Heat/H2O2-NaClO2 were proposed finally.

Research on sulfur oxides and nitric oxides released from coal-fired flue gas and vehicle exhaust: a bibliometric analysis.

A bibliometric method was used to evaluate the global scientific publications about sulfur oxides and nitric oxides released by coal-fired flue gas and vehicle exhaust from 1995 to 2018 and to provide insights into the characteristics of the articles and tendencies that may exist in the publications. Performance of publications, research tendency, and hotspots were analyzed. The article number had an explosive growth in 2004 and, then, began to grow steadily. China had an absolutely advantage in publication quantities; however, America had a leading position considering publication cited times. The simultaneous removal of mercury, particulate matter, and CO2 was a research hotpot in sulfur oxide and nitric oxide control process; oxidation, absorption, and catalytic reduction were the central control methods that had the most strength in relation with sulfur dioxide and nitric oxide. Considering the study of traditional flue gas pollutant control method (limestone-gypsum method, selective catalytic reduction, etc.) was perfection, it was speculated that adsorption by ionic liquid, electricity charging, advanced oxidation progress, and multi-pollutant removal, simultaneously, would be the new research orientation in flue gas pollutant control. One of the hot points of controlling the vehicle exhaust was the application of the "green energy" biodiesel; lots of keywords concerning human health suggested that quite a lot studies were focused on the health hazard brought by sulfur oxides and nitric oxide.

Removal of multi-pollutant from flue gas utilizing ammonium persulfate solution catalyzed by Fe/ZSM-5.

A nano-sized iron loaded ZSM-5 zeolite (Fe/ZSM-5) catalyst was firstly used to activate (NH4)2S2O8 solution for the simultaneous removal of multi-pollutant from flue gas. The simultaneous removal efficiencies 100% of SO2, 72.6% of NO and 93.4% of Hg° were achieved under the condition that the catalyst dose was 0.8 g/L, concentration, pH and temperature of (NH4)2S2O8 solution were 0.03 mol/L, 5 and 65 °C, respectively. The stability of catalyst was checked by a continuous test, proving that the catalytic activity was maintained for 4 h and the leached iron reached low levels. Based on the catalyst characterizations, product analysis and literatures, the removal mechanism was speculated preliminarily, during which, OH and SO4- played key roles for oxidizing NO and Hg° into NO3- and Hg2+.

Simultaneous removal of NO and SO2 from flue gas using vaporized H2O2 catalyzed by nanoscale zero-valent iron.

To remove NO and SO2 from flue gas simultaneously, a heterogeneous catalytic oxidation system was developed with the nanoscale zero-valent iron (nZVI), vaporized H2O2, and sodium humate (HA-Na) acting as the catalyst, oxidant, and absorbent, respectively. The experimental results indicated that the desulfurization was mainly influenced by the absorption, and the denitrification was significantly affected by the catalytic oxidation parameters. Under the optimal conditions, the simultaneous removal efficiencies of SO2 and NO were 100 and 88.4%, respectively. The presence of ·OH during the removal process was proved by the scavenger tests, and the production of ·OH with and without nZVI was indirectly evaluated by the electron paramagnetic resonance (EPR) and methylene blue experiments. Moreover, the fresh and aged nZVI were characterized by a series of techniques and the results suggested that the redox pair Fe2+/Fe3+ released by nZVI could react with H2O2 to provide the sustainable ·OH, which was important for the oxidation from NO and SO2 to NO3- and SO42-. The removal mechanism was proposed preliminarily based on the correlative experiments, characterizations, and references.

Simultaneous removal of multi-pollutants from flue gas by a vaporized composite absorbent.

An economical process that was used to remove SO2, NO and Hg0 simultaneously was developed, based on the pre-oxidations of Hg0 and NO by a vaporized Fenton-based complex oxidant (FO) consisted of Fenton and NaClO. The effects of concentrations of FeSO4 and NaClO in the oxidant, the molar ratio of vaporized oxidant to multi-pollutant, the oxidant solution pH, the reaction temperature, the gas flow ratio of vaporized FO to multi-pollutants, the flue gas flow and the concentrations of coexistence gases in flue gas on the simultaneous removals were investigated experimentally. The results showed that the removals of NO and Hg0 were significantly depended on FeSO4 and NaClO concentrations, the molar ratio of vaporized oxidant to multi-pollutants, the FO solution pH, the reaction temperature, the gas flow ratio of vaporized FO to multi-pollutants and flue gas flow. And higher concentration of SO2 and an appropriate concentration of NO had the promotion for Hg0 removal. The average simultaneous removal efficiencies of 100% for SO2, 81% for NO and 91% for Hg0 were obtained under the optimal reaction conditions. According to the characterization of the reaction removal products by SEM, EDS, XRD and AFS, the reaction mechanism was speculated.