Zan Qu

Catalytic Oxidation of Elemental Mercury over the Modified Catalyst Mn/α-Al2O3 at Lower Temperatures

In order to facilitate the removal of elemental mercury (Hg(0)) from coal-fired flue gas, catalytic oxidation of Hg(0) with manganese oxides supported on inert alumina (alpha-Al2O3) was investigated at lower temperatures (373-473 K). To improve the catalytic activity and the sulfur-tolerance of the catalysts at lower temperatures, several metal elements were employed as dopants to modify the catalyst of Mn/alpha-Al2O3. The best performance among the tested elements was achieved with molybdenum (Mo) as the dopant in the catalysts. It can work even better than the noble metal catalyst Pd/alpha-Al2O3. Additionally, the Mo doped catalyst displayed excellent sulfur-tolerance performance at lower temperatures, and the catalytic oxidation efficiency for Mo(0.03)-Mn/alpha-Al2O3 was over 95% in the presence of 500 ppm SO2 versus only about 48% for the unmodified catalyst. The apparent catalytic reaction rate constant increased by approximately 5.5 times at 423 K. In addition, the possible mechanisms involved in Hg(0) oxidation and the reaction with the Mo modified catalyst have been discussed.

Gaseous Elemental Mercury Capture from Flue Gas Using Magnetic Nanosized (Fe3-xMnx)1-δO4

A series of nanosized (Fe3-xMnx)1-δO4 (x = 0, 0.2, 0.5, and 0.8) were synthesized for elemental mercury capture from the flue gas. Cation vacancies on (Fe3-xMnx)1-δO4 can provide the active sites for elemental mercury adsorption, and Mn(4+) cations on (Fe3-xMnx)1-δO4 may be the oxidizing agents for elemental mercury oxidization. With the increase of Mn content in the spinel structure, the percents of Mn(4+) cations and cation vacancies on the surface increased. As a result, elemental mercury capture by (Fe3-xMnx)1-δO4 was obviously promoted with the increase of Mn content. (Fe2.2Mn0.8)1-δO4 showed an excellent capacity for elemental mercury capture (>1.5 mg g(-1) at 100-300 °C) in the presence of SO2 and HCl. Furthermore, (Fe2.2Mn0.8)1-δO4 with the saturation magnetization of 45.6 emu g(-1) can be separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed Hg. Therefore, nanosized (Fe2.2Mn0.8)1-δO4 may be a promising sorbent for the control of elemental mercury emission.

Significance of RuO2 Modified SCR Catalyst for Elemental Mercury Oxidation in Coal-fired Flue Gas

Catalytic conversion of elemental mercury (Hg(0)) to its oxidized form has been considered as an effective way to enhance mercury removal from coal-fired power plants. In order to make good use of the existing selective catalytic reduction of NO(x) (SCR) catalysts as a cobenefit of Hg(0) conversion at lower level HCl in flue gas, various catalysts supported on titanium dioxide (TiO(2)) and commercial SCR catalysts were investigated at various cases. Among the tested catalysts, ruthenium oxides (RuO(2)) not only showed rather high catalytic activity on Hg(0) oxidation by itself, but also appeared to be well cooperative with the commercial SCR catalyst for Hg(0) conversion. In addition, the modified SCR catalyst with RuO(2) displayed an excellent tolerance to SO(2) and ammonia without any distinct negative effects on NO(x) reduction and SO(2) conversion. The demanded HCl concentration for Hg(0) oxidation can be reduced dramatically, and Hg(0) oxidation efficiency over RuO(2) doped SCR catalyst was over 90% even at about 5 ppm HCl in the simulated gases. Ru modified SCR catalyst shows a promising prospect for the cobenefit of mercury emission control.

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).

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

The equilibria and kinetics of the reaction between bromine (Br(2)) and chlorine (Cl(2)) to form bromine chloride (BrCl) at various temperatures were determined. BrCl was employed to oxidize elemental mercury (Hg(0)) under simulated flue gas conditions. The removal of Hg(0) from the gas phase by a homogeneous gas-phase oxidation reaction and the heterogeneous reactions involving flyash were investigated. The second-order gas phase rate constant was determined to be 2.3(+/-0.2) x 10(-17) cm(3).molecules(-1).s(-1) at 373K. The reaction of Hg(0)/BrCl was significantly accelerated in the presence of flyash, and the estimated Hg(0) removal efficiency in the presence of 0.6 ppmv BrCl and 20 g/m(3) flyash was up to 90%. Unexpectedly, the major product was found to be HgCl(2), rather than HgBr(2), indicating that bromine in part acted as the accelerant in Hg(0) oxidation in BrCl/Br(2)/Cl(2) system by facilitating the formation of intermediates. As a result, bromine consumption is much less than if only bromine gas is utilized alone. These results were helpful not only for understanding the mechanism of Hg(0) removal in coal-fired flue gas but also in any atmosphere in which bromine and chlorine species coexist.

Mechanism of the Selective Catalytic Oxidation of Slip Ammonia over Ru-Modified Ce–Zr Complexes Determined by in Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy

The slip ammonia from selective catalytic reduction (SCR) of NOx in coal-fired flue gas can result in deterioration of the utilities or even the environmental issues. To achieve selective catalytic oxidation (SCO) of slip ammonia, Ru-modified Ce-Zr solid solution catalysts were prepared and evaluated under various conditions. It was found that the Ru/Ce(0.6)Zr(0.4)O2(polyvinylpyrrolidone (PVP)) catalyst displayed significant catalytic activity and the slip ammonia was almost completely removed with the coexistence of NOx and SO2. Interestingly, the effect of SO2 on NH3 oxidation was bifacial, and the N2 selectivity of the resulting products was as high as 100% in the presence of SO2 and NH3. The mechanism of the SCO of NH3 over Ru/Ce(0.6)Zr(0.4)O2(PVP) was studied using various techniques, and the results showed that NH3 oxidation follows an internal SCR (iSCR) mechanism. The adsorbed ammonia was first activated and reacted with lattice oxygen atoms to form an -HNO intermediate. Then, the -HNO mainly reacted with atomic oxygen from O2 to form NO. Meanwhile, the formed NO interacted with -NH2 to N2 with N2O as the byproduct, but the presence of SO2 can effectively inhibit the production of N2O.

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.

Oxidation and Stabilization of Elemental Mercury from Coal-Fired Flue Gas by Sulfur Monobromide

Sulfur monobromide (S(2)Br(2)) was employed as a task-specific oxidant to capture and stabilize elemental mercury from coal-fired flue gas. Its performances on the removal of Hg(0) were investigated with respect to the gas-phase reaction and particle-involved reactions. It was found that the gas-phase reaction between Hg(0) and S(2)Br(2) was rapid, and the determined second-rate constant was about 1.2(+/-0.2) x 10(-17)cm(3) molecules(-1) s(-1) at 373 K, which was about 30 times higher than that with sulfur monochloride. The pilot tests showed that the presence of fly ash in flue gas can accelerate the removal of Hg(0) significantly. It was predicted that about 90% of Hg(0) removal efficiency can be obtained with 0.6 ppmv S(2)Br(2) and 30 g/m(3) fly ash in flue gas, and the unburned carbon in fly ash played an important role for Hg(0) removal. The fates of S(2)Br(2) and mercury in the process were evaluated, and the product analysis and leaching tests indicated that mercuric sulfide was the main product of the converted Hg(0) by the direct reaction and consequent series reactions, which is more stable and less toxic than other mercury species. Also, the surplus S(2)Br(2) in flue gas could be captured and neutralized effectively by the alkali components in fly ash or FGD liquor, and its hydrolysis products (elemental sulfur and sulfide) were also helpful to the stabilization of mercury. The result indicated that S(2)Br(2) is a promising oxidant for elemental mercury (Hg(0)) oxidation and stabilization for mercury emission control.

Novel Effective Catalyst for Elemental Mercury Removal from Coal-Fired Flue Gas and the Mechanism Investigation

Mercury pollution from coal-fired power plants has drawn attention worldwide. To achieve efficient catalytic oxidation of Hg(0) at both high and low temperatures, we prepared and tested novel IrO2 modified Ce-Zr solid solution catalysts under various conditions. It was found that the IrO2/Ce0.6Zr0.4O2 catalyst, which was prepared using the polyvinylpyrrolidone-assisted sol-gel method, displayed significantly higher catalytic activity for Hg(0) oxidation. The mechanism of Hg(0) removal over IrO2/Ce0.6Zr0.4O2 was studied using various methods, and the Hg(0) oxidation reaction was found to follow two possible pathways. For the new chemisorption-regeneration mechanism proposed in this study, the adsorbed Hg(0) was first oxidized with surface chemisorbed oxygen species to form HgO; the HgO could desorb from the surface of catalysts by itself or react with adsorbed HCl to be release in the form of gaseous HgCl2. O2 is indispensable for the chemisorption process, and the doping of IrO2 could facilitate the chemisorption process. In addition, the Deacon reaction mechanism was also feasible for Hg(0) oxidation: this reaction would involve first oxidizing the adsorbed HCl to active Cl species, after which the Hg(0) could react with Cl to form HgCl2. Additionally, doping IrO2 could significantly improve the Cl yield process. In summary, the novel IrO2 modified catalyst displayed excellent catalytic activity for elemental mercury oxidation, and the proposed reaction mechanisms were determined reasonably.

[MoS4]2– Cluster Bridges in Co–Fe Layered Double Hydroxides for Mercury Uptake from S–Hg Mixed Flue Gas

[MoS4]2- clusters were bridged between CoFe layered double hydroxide (LDH) layers using the ion-exchange method. [MoS4]2-/CoFe-LDH showed excellent Hg0 removal performance under low and high concentrations of SO2, highlighting the potential for such material in S-Hg mixed flue gas purification. The maximum mercury capacity was as high as 16.39 mg/g. The structure and physical-chemical properties of [MoS4]2-/CoFe-LDH composites were characterized with FT-IR, XRD, TEM&SEM, XPS, and H2-TPR. [MoS4]2- clusters intercalated into the CoFe-LDH layered sheets; then, we enlarged the layer-to-layer spacing (from 0.622 to 0.880 nm) and enlarged the surface area (from 41.4 m2/g to 112.1 m2/g) of the composite. During the adsorption process, the interlayer [MoS4]2- cluster was the primary active site for mercury uptake. The adsorbed mercury existed as HgS on the material surface. The absence of active oxygen results in a composite with high sulfur resistance. Due to its high efficiency and SO2 resistance, [MoS4]2-/CoFe-LDH is a promising adsorbent for mercury uptake from S-Hg mixed flue gas.