Novel synthesis of fly-ash-derived Cu-loaded SAPO-34 catalysts and their use in selective catalytic reduction of NO with NH3

A combined acid–alkali hydrothermal method was used to prepare fly ash–derived SAPO-34 molecular sieves from a thermal power plant in Inner Mongolia(China).The specific surface area of the prepared fly-ash-derived SAPO-34 molecular sieves was 579 m^2 g^-1,the total pore volume was about 0.27 cm^3 g^-1,and the pore size was 0.56 nm;the molar ratios of Al2O3:P2O5:SiO2 were 1:0.86:0.45.Cu/SAPO-34 catalysts were prepared by impregnation of low-cost fly-ash-derived SAPO-34 molecular sieves as a support and tested in selective catalytic reduction with NH3(NH3-SCR).Powder X-ray diffraction(XRD),N2 adsorption–desorption,X-ray photoelectron spectroscopy(XPS),H2 temperatureprogrammed reduction(H2-TPR),NH3 temperature-programmed desorption(NH3-TPD),electron paramagnetic resonance(EPR),nuclear magnetic resonance(NMR),X-ray fluorescence analysis(XRF)and scanning electron microscopy(SEM)were used for catalyst characterization and investigation of the relationships between the catalyst structure and the catalytic activity.The actual silica:alumina ratio of the molecular sieves did not increase with increasing Cu loading,indicating that increasing the Cu loading does not change the original structure of the SAPO-34 molecular sieves.The XRF and NMR results showed that replacement by Cu results in more Si islands.The molecular sieve acidity decreased because of the increased number of Si islands.The NH3-TPD results showed that for the Cu/SAPO-34 catalysts there was a low correlation between the low-temperature activity and the amount of acidic sites.SCR activity is closely related to the location of Cu.The 4.47 Cu/SAPO-34 catalyst has the highest isolated Cu2+showed the highest NH3-SCR activities(>90%)at 250–350℃.This work opens up new avenues for recycling fly ash formed in coal-fired power plants(reducing environmental pollution)and developing low-cost SCR catalysts for NOx pollution control.

The relative changes of a sea surface temperature in the South China Sea since the Pliocene

The reconstruction of sea surface temperature(SST) is a key issue in research on paleoceanography. The recently related studies are mainly concentrated on the Quaternary. The skeletons of a typical species of benthonic foraminifer(Amphistegina radiata) in the top 0–375.30 m interval of Well "Xike-1" reef core, Shidao Island, the Xisha Islands, are uniformly selected. The ratios of magnesium to calcium concentrations and other indicators are analyzed by an electron microprobe analysis(EMPA) with the purpose of estimating the paleo-SSTs since the Pliocene and further investigating the periodic change law of paleoclimate in the South China Sea(SCS).Meanwhile, the geologic significance of paleoclimatic events in the SCS is discussed with global perspectives. The results indicate that the paleo-SSTs reconstructed by the ratios of magnesium to calcium concentrations in the SCS show a general periodic trend of "high–low–high–low" in values changes since the Pliocene. By comparison,the fluctuations of reconstructed paleo-SSTs are much stronger in the Quaternary. Moreover, the variations of the ratios of magnesium to calcium concentrations in the A. radiata skeletons have recorded a series of major paleoclimatic events since the Pliocene, of which the Quaternary glaciation events and the Arctic ice cap forming events during the late Pliocene are more significant. Thus, using the changes of the ratios of magnesium to calcium concentrations in the A. radiata skeletons from Well "Xike-1" reef core to reflect the relative changes of paleo-SSTs is a relatively feasible and reliable way in the SCS, which is also proved by the correlation of drilling cores characteristics in this area.

Astronomical tuning and magnetostratigraphy of Neogene biogenic reefs in Xisha Islands, South China Sea

Biogenic reefs are one of two major depositional types in the South China Sea, and are constructed by coral, algae and bryozoa. The West Pacific is a major area of biogenic reef development and plays a critical role in the global carbon cycle. However, the lack of geochronological studies in previous works inhibits our understanding of their contributions. Herein, we conduct a cyclostratigraphic and magnetostratigraphic study on Neogene biogenic reefs using the XK–1 core that was drilled at the Shidao Island,Xisha(Paracel) Islands. The main findings of this study are:(1) the establishment of reliable magentostratigraphy for Ledong, Huangliu, Meishan and Sanya Formations;(2) the magnetic susceptibility variation can be inferred as growth index and tuned to the 405–ka long eccentricity cycle;(3) the astronomical geochronology suggests that the bottom ages for Ledong, Yinggehai, Huangliu, Meishan,and Sanya Formations are 2.2 Ma, 5.7 Ma, 10.4 Ma, 16.6 Ma, and 24.3 Ma, respectively; and (4) Earth's eccentricity and obliquity played predominant roles in biogenic reef establishment on orbital to tectonic timescales. Thus, the reported geochronology offers an opportunity to test the contributions of various factors and hypothesize their roles in the global carbon cycle in future.

VxMn(4-x)Mo3Ce3/Ti catalysts for selective catalytic reduction of NO by NH3

A series of vanadium based catalysts(VxMn(4-x)Mo3Ce3/Ti) with different vanadium(x wt.%) and manganese((4-x) wt.%) contents have been prepared by the wet impregnation method and investigated for selective catalytic reduction(SCR) of NOx by NH3 in the presence of 8 vol.% H2O and 500 ppm V SO2.The physicochemical characteristics of the catalysts were thoroughly characterized.The SCR of NOx by NH3(NH3-SCR) activity, especially the low-temperature activity, significantly increased with increasing V2O5 content in the catalyst until the V2O5 content reached 1.5 wt.%, which corresponds well with the redox properties of the catalyst.All of the metal oxides were well dispersed and strongly interacted with each other on the catalyst surface.V mainly exists in the V^5+state in the catalysts.The strong synergistic effect between the vanadium and cerium species led to formation of more Ce^3+species, and that between the vanadium and manganese species contributed to formation of more manganese species with low valences.All of the catalysts exhibited strong acidity, while the redox properties determined the NH3-SCR activity, especially the low-temperature activity.H2O and SO2 had severe inhibiting effects on the activity of V1.5Mn2.5Mo3Ce3/Ti.However, good H2O and SO2 resistance and high NOx conversion by V1.5Mn2.5Mo3Ce3/Ti could be achieved in the presence of SO2 and almost no decline was observed in a long-term test at 275℃ for 168 hr in the presence of SO2 and H2O, which can be attributed to the sulfate species formed on the catalyst surface.

Effects of MOx(M=Mn,Cu,Sb,La)on V-Mo-Ce/Ti selective catalytic reduction catalysts

A series of MOx-V2O5-MoO3-CeO2/TiO2(M=Mn,Cu,Sb,and La) catalysts were prepared via an impregnation method.The physico-chemical properties of the catalysts were characterized and their NH3-SCR of NO performance was compared.The Mn-loaded catalyst(Mn5V1Mo3Ce7/Ti) exhibits a large number of acid sites of varying strength,and together with good reducibility of the catalyst,contributes to the optimal SCR performance.The sulphate species formed in the presence of SO2 significantly enhance the H2O and SO2 tolerance of Mn5V1Mo3Ce7/Ti.The Cu-loaded catalyst(Cu5V1Mo3Ce7/Ti)demonstrates potential in flue gas applications in the absence of SO2 at low temperatures because of the excellent redox ability observed and the high degree of weak acid sites.The Sb and La loaded catalysts(Sb5V1Mo3Ce7/Ti and La5V1Mo3Ce7/Ti),especially La5V1Mo3 Ce7/Ti,exhibit the largest number of acid sites and the lowest reducibility,and therefore,may be suitable for use in high temperature denitrification applications.

Effect of manganese and/or ceria loading on V_2O_5-MoO_3/TiO_2 NH_3 selective catalytic reduction catalyst

The effect of manganese and/or ceria loading of V2 O5-MoO3/TiO2 catalysts was investigated for selective catalytic reduction(SCR) of NOx by NH3.The manganese and/or ceria loaded V2 O5-MoO3/TiO2 catalysts we re prepared by the wetness impregnation method.The physicochemical characteristics of the catalysts were thoroughly characterized.The catalytic performance of 1.5 wt% V2 O5-3 wt% MoO3/TiO2(V1.5 Mo3/Ti) is greatly enhanced by addition of 2.5 wt% MnOx and 3.0 wt% CeO2(V1.5 Mo3 Mn2.5 Ce3/Ti) below450℃.Compared with the V1.5 Mo3/Ti catalyst with NOx conversion of 75% at 275 ℃,V1.5 Mo3 Mn2.5 Ce3/Ti exhibits higher NOx conversion of 84% with good resistance to SO2 and H2 O at a gas hourly space velocity value of 150000 h-1.The active manganese,cerium,molybdenum,and vanadium oxide species are highly dispersed on the catalyst surface and some synergistic effects exist among these species.Addition of MnOx significantly enhances the redox ability of the cerium,vanadium,and molybdenum species.Addition of Ce increases the acidity of the catalyst.More active oxygen species,including surface chemisorbed oxygen,form with addition of Mn and/or Ce.Because of the synergistic effects,appropriate proportions of manganese in different valence states exist in the catalysts.In summary,the good redox ability and the strong acidity contribute to the high NH3-SCR activity and N2 selectivity of the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst in a wide temperature range.And the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst shows good resistance to H2 O and SO2 in long-time catalytic testing,which can be ascribed to the highly sulfated species adsorbed on the catalyst.