Haomiao Xu

MnOx/Graphene for the Catalytic Oxidation and Adsorption of Elemental Mercury.

MnOx/graphene composites were prepared and employed to enhance the performance of manganese oxide (MnOx) for the capture of elemental mercury (Hg(0)) in flue gas. The composites were characterized using FT-IR, XPS, XRD, and TEM, and the results showed that the highly dispersed MnOx particles could be readily deposited on graphene nanosheets via hydrothermal process described here. Graphene appeared to be an ideal support for MnOx particles and electron transfer channels in the catalytic oxidation of Hg(0) at a high efficiency. Thus, MnOx/graphene-30% sorbents exhibited an Hg(0) removal efficiency of greater than 90% at 150 °C under 4% O2, compared with the 50% removal efficiency of pure MnOx. The mechanism of Hg(0) capture is discussed, and the main Hg(0) capture mechanisms of MnOx/graphene were catalytic oxidation and adsorption. Mn is the main active site for Hg(0) catalytic oxidation, during which high valence Mn (Mn(4+) or Mn(3+)) is converted to low valence Mn (Mn(3+) or Mn(2+)). Graphene enhanced the electrical conductivity of MnOx, which is beneficial for catalytic oxidation. Furthermore, MnOx/graphene exhibited an excellent regenerative ability, and is a promising sorbent for capturing Hg(0).

Different crystal-forms of one-dimensional MnO2 nanomaterials for the catalytic oxidation and adsorption of elemental mercury

MnO2 has been found to be a promising material to capture elemental mercury (Hg(0)) from waste gases. To investigate the structure effect on Hg(0) uptake, three types of one-dimensional (1D) MnO2 nano-particles, α-, β- and γ-MnO2, were successfully prepared and tested. The structures of α-, β- and γ-MnO2 were characterized by XRD, BET, TEM and SEM. The results indicate that α-, β- and γ-MnO2 were present in the morphologies of belt-, rod- and spindle-like 1D materials, respectively. These findings demonstrated noticeably different activities in capturing Hg(0), depending on the surface area and crystalline structure. The performance enhancement is in the order of: β-MnO2<γ-MnO2<α-MnO2 at 150°C. The mechanism for Hg(0) removal using MnO2 was discussed with the help of results from H2-TPR, XPS and Hg(0) removal experiments in the absence of O2. It was determined that the oxidizability of three forms of MnO2 increased as follows: β-MnO2<γ-MnO2<α-MnO2. The mechanism for Hg(0) capture was ascribed to the Hg(0) catalytic oxidation with the reduction of Mn(4+)→Mn(3+)→Mn(2+). Furthermore, the interaction forces between mercury and manganese oxide sites are demonstrated to increase in the following order: β-MnO2<γ-MnO2<α-MnO2 based on the desorption tests.

Sn–Mn binary metal oxides as non-carbon sorbent for mercury removal in a wide-temperature window

A series of Sn-Mn binary metal oxides were prepared through co-precipitation method. The sorbents were characterized by powder X-ray diffraction (powder XRD), transmission electronic microscopy (TEM), H2-temperature-programmed reduction (H2-TPR) and NH3-temperature-programmed desorption (NH3-TPD) methods. The capability of the prepared sorbents for mercury adsorption from simulated flue gas was investigated by fixed-bed experiments. Results showed that mercury adsorption on pure SnO2 particles was negligible in the test temperature range, comparatively, mercury capacity on MnOx at low temperature was relative high, but the capacity would decrease significantly when the temperature was elevated. Interestingly, for Sn-Mn binary metal oxide, mercury capacity increased not only at low temperature but also at high temperature. Furthermore, the impact of SO2 on mercury adsorption capability of Sn-Mn binary metal oxides was also investigated and it was noted that the effect at low temperature was different comparing with that of high temperature. The mechanism was investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs). Moreover, a mathematic model was built to calculate mercury desorption activation energy from Sn to Mn binary metal oxides.

Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review

Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. Mn-based oxides can be classified into four types: (1) single manganese oxide (MnOx), (2) supported manganese oxide (MnOx/support), (3) composite manganese oxides (MnOx-X), and (4) special crystalline manganese oxides (S-MnOx). These Mn-based oxides have been widely used as catalysts for the elimination of gaseous pollutants. This review aims to describe the environmental applications of these manganese oxides and provide perspectives. It gives detailed descriptions of environmental applications of the selective catalytic reduction of NOx with NH3, the catalytic combustion of volatile organic compounds, Hg0 oxidation and adsorption, and soot oxidation, in addition to some other environmental applications. Furthermore, this review mainly focuses on the effects of structure, morphology, and modified elements and on the role of catalyst supports in gaseous heterogeneous catalytic reactions. Finally, future research directions for developing manganese oxide catalysts are proposed.

A novel method for the sequential removal and separation of multiple heavy metals from wastewater

A novel method was developed and applied for the treatment of simulated wastewater containing multiple heavy metals. A sorbent of ZnS nanocrystals (NCs) was synthesized and showed extraordinary performance for the removal of Hg2+, Cu2+, Pb2+ and Cd2+. The removal efficiencies of Hg2+, Cu2+, Pb2+ and Cd2+ were 99.9%, 99.9%, 90.8% and 66.3%, respectively. Meanwhile, it was determined that solubility product (Ksp) of heavy metal sulfides was closely related to adsorption selectivity of various heavy metals on the sorbent. The removal efficiency of Hg2+ was higher than that of Cd2+, while the Ksp of HgS was lower than that of CdS. It indicated that preferential adsorption of heavy metals occurred when the Ksp of the heavy metal sulfide was lower. In addition, the differences in the Ksp of heavy metal sulfides allowed for the exchange of heavy metals, indicating the potential application for the sequential removal and separation of heavy metals from wastewater. According to the cumulative adsorption experimental results, multiple heavy metals were sequentially adsorbed and separated from the simulated wastewater in the order of the Ksp of their sulfides. This method holds the promise of sequentially removing and separating multiple heavy metals from wastewater.

Design of 3D MnO2/Carbon sphere composite for the catalytic oxidation and adsorption of elemental mercury

Three-dimensional (3D) MnO2/Carbon Sphere (MnO2/CS) composite was synthesized from zero-dimensional carbon spheres and one-dimensional α-MnO2 using hydrothermal method. The hierarchical MnO2/CS composite was applied for the catalytic oxidation and adsorption of elemental mercury (Hg0) from coal-fired flue gas. The characterization results indicated that this composite exhibits a 3D urchin morphology. Carbon spheres act as the core and α-MnO2 nano-rods grew on the surface of carbon spheres. This 3D hierarchical structure benefits the enlargement of surface areas and pore volumes. Hg0 removal experimental results indicated that the MnO2/CS composite has an outstanding Hg0 removal performance due to the higher catalytic oxidation and adsorption performance. MnO2/CS composite had higher than 99% Hg0 removal efficiency even after 600min reaction. In addition, the nano-sized MnO2/CS composite exhibited better SO2 resistance than pure α-MnO2. Moreover, the Hg-TPD results indicated that the adsorbed mercury can release from the surface of MnO2/CS using a thermal decomposition method.

Stabilization of mercury over Mn-based oxides: Speciation and reactivity by temperature programmed desorption analysis.

Mercury temperature-programmed desorption (Hg-TPD) method was employed to clarify mercury species over Mn-based oxides. The elemental mercury (Hg0) removal mechanism over MnOx was ascribed to chemical-adsorption. HgO was the primary mercury chemical compound adsorbed on the surface of MnOx. Rare earth element (Ce), main group element (Sn) and transition metal elements (Zr and Fe) were chosen for the modification of MnOx. Hg-TPD results indicated that the binding strength of mercury on these binary oxides followed the order of Sn-MnOx<Ce-MnOx∼MnOx<Fe-MnOx<Zr-MnOx. The activation energies for desorption were calculated and they were 64.34, 101.85, 46.32, 117.14, and 106.92eV corresponding to MnOx, Ce-MnOx, Sn-MnOx, Zr-MnOx and Fe-MnOx, respectively. Sn-MnOx had a weak bond of mercury (Hg-O), while Zr-MnOx had a strong bond (HgO). Ce-MnOx and Fe-MnOx had similar bonds compared with pure MnOx. Moreover, the effects of SO2 and NO were investigated based on Hg-TPD analysis. SO2 had a poison effect on Hg0 removal, and the weak bond of mercury can be easily destroyed by SO2. NO was favorable for Hg0 removal, and the bond strength of mercury was enhanced.

Investigation on mercury removal method from flue gas in the presence of sulfur dioxide

A new integrated process was developed for the removal and reclamation of mercury from the flue gas in the presence of SO2, typically derived from nonferrous metal smelting. The new process contains a pre-desulfurization unit (Stage I) and a co-absorption unit (Stage II). In Stage I, 90% of the SO2 from flue gas can be efficiently absorbed by ferric sulfate and reclaimed sulfuric acid. Meanwhile, the proportion of Hg(2+) and Hg(0) in the flue gas can be redistributed in this stage. Then, over 95% of the Hg(0) and the residual SO2 can be removed simultaneously with a composite absorption solution from the flue gas in Stage II, which is much more efficient for the Hg(0) reclaiming than the traditional method. The composite absorption solution in Stage II, which is composed of 0.1g/L HgSO4, 1.0% H2O2 and H2SO4, could effectively remove and reclaim Hg(0) overcoming the negative effect of SO2 on Hg(0) absorption. Moreover, the concentrations of HgSO4 and H2O2 were adjusted with the changes in of the concentrations of Hg(0) and SO2 in the flue gas. It is a potential and promising technology for the mercury removal and reclaim from the flue gas in the presence of SO2.

Design of MnO2/CeO2-MnO2 hierarchical binary oxides for elemental mercury removal from coal-fired flue gas

MnO2/CeO2-MnO2 hierarchical binary oxide was synthesized for elemental mercury (Hg0) removal from coal-fired flue gas. CeO2 in-situ grow on the surface of carbon spheres, and that CeO2@CSs acted as precursor for porous MnO2/CeO2-MnO2. XRD, Raman, XPS, FT-IR, and H2-TPR were selected for the physical structural and chemical surface analysis. The results indicated that the composite has sufficient surface oxygen and hierarchical porous structure. The Hg0 removal experiments results indicated that MnO2/CeO2-MnO2 exhibited excellent Hg0 removal performance, with an 89% removal efficiency of total 300min at 150°C under 4% O2. MnO2 was the primary active site for Hg0 catalytic oxidation. The porous structure was beneficial for gaseous mercury physically adsorption. In addition, CeO2 enhanced the oxygen capture performance of the composite and the oxidation performance for MnO2. Moreover, the effects of O2, SO2 and H2O were also tested in this study. O2 promoted the Hg0 removal reaction. While SO2 and H2O can poison the MnO2 active site, resulted in a low Hg0 removal efficiency.

Research of mercury removal from sintering flue gas of iron and steel by the open metal site of Mil-101(Cr)

Metal-organic frameworks (MOFs) adsorbent Mil-101(Cr) was introduced for the removal of elemental mercury from sintering flue gas. Physical and chemical characterization of the adsorbents showed that MIL-101(Cr) had the largest BET surface area, high thermal stability and oxidation capacity. Hg0 removal performance analysis indicated that the Hg0 removal efficiency of MIL-101(Cr) increased with the increasing temperature and oxygen content. Besides, MIL-101(Cr) had the highest Hg0 removal performance compared with Cu-BTC, UiO-66 and activated carbon, which can reach about 88% at 250 °C. The XPS and Hg-TPD methods were used to analyze the Hg0 removal mechanism; the results show that Hg0 was first adsorbed on the surface of Mil-101(Cr), and then oxidized by the open metal site Cr3+. The generated Hg2+ was then combined surface adsorbed oxygen of adsorbent to form HgO, and the open metal site Cr2+ was oxidized to Cr3+ by surface active oxygen again. Furthermore, MIL-101(Cr) had good chemical and thermal stability.