Study of S poisoning mechanism on LaMnO3 perovskite catalyst surface based on DFT method.

The sulfur poisoning mechanism of low-temperature SCR de-NOx catalyst has always been one of the hot spots in academic circles. By studying the surface sulfur poisoning mechanism, low-temperature catalysts can be developed pertinently. In this paper, the mechanism of sulfur poisoning on the surface of LaMnO3 catalyst was studied by DFT method, and the adsorption process of sulfur oxides on the surface and its influence on SCR reaction process, as well as the morphology and decomposition process of ammonium sulfate on the surface were calculated. The results show that sulfur oxides will be adsorbed on the surface and occupy the adsorption site, which will adversely affect the subsequent SCR reaction. At the same time, ammonium sulfate will accumulate on the catalyst surface, which will lead to sulfur poisoning.

Combination of sequencing batch reactor activated sludge process with sludge lysis using thermophilic bacterial community for minimizing excess sludge.

Sludge reduction is a major challenge in biological wastewater treatment. Hydrolytic enzymes secreted by thermophilic bacteria can lyse sludge and thus achieve sludge reduction, and the indigenous thermophilic community in sludge can lyse sludge more effectively. In this study, the feasibility of combining a sludge lysis reactor based on thermophilic bacteria community (LTBC reactor, 75 °C) with a conventional sequencing batch activated sludge reactor (SBR) for sludge reduction (i.e., LTBC-SBR process) was systematically investigated first time. The effect of lysed sludge returning to the biochemical tank on pollutant removal efficiency, sludge flocculation, sludge settling, and microbial community and function of the LTBC-SBR process was studied. In the LTBC1-SBR process, a sludge growth rate of 0.71 g TSS/day was observed when the lysed sludge reflux ratio (LRR) was 1, and the sludge generation was reduced by 81.5% compared to the conventional SBR reactor. In the LTBC1-SBR process, the removal efficiencies of chemical oxygen demand and total nitrogen were 94.0% and 80.5%, respectively. There was no significant difference in the sludge volume index from the SBR to the LTBC1-SBR stage, however, the effluent suspended solids concentration increased from 35.2 ± 2.1 mg/L to 80.1 ± 5.3 mg/L. This was attributed to the reflux of sludge lysate. In addition, the changes in extracellular polymers content and composition resulted in poor sludge flocculation performance. Heterotrophic bacteria associated with Actinobacteria and Patescibacteria enriched in LTBC1-SBR with relative abundance of 28.51 ± 1.25% and 20.01 ± 1.21%, respectively, which decomposed the macromolecules in the refluxed lysed sludge and contributed to the sludge reduction. Furthermore, due to the inhibition of nitrite-oxidizing bacteria, the nitrite concentration in the effluent of the LTBC1-SBR system reached 4.7 ± 1.1 mg/L, and part of the denitrification process was achieved by short-cut nitrification and simultaneous denitrification. These results indicate that in-situ sludge reduction technology based on lyse sludge lysing by thermophilic community has considerable potential to be widely used in wastewater treatment.

Excellent operating temperature window and H2O/SO2 resistances of Fe-Ce catalyst modified by different sulfation strategies for NH3-SCR reaction.

Expecting to gain an excellent operating temperature window and superior catalytic activity of the catalyst in SCR reaction, the Fe-Ce bimetallic oxide catalyst was firstly prepared and sulfated with two different sulfation strategies by H2SO4. It is interestingly found that both the two sulfation strategies can significantly broaden the operating temperature window of the catalyst. In particular, the SFC and FCS both exhibit superior resistance to H2O + SO2, and the NOx conversion of the SFC even displays no changes in the coexistence of H2O and SO2. The characterization results show that different sulfation strategies can generate amorphous sulfate species rather than bulk sulfate species. Furthermore, more surface-adsorbed oxygen as well as higher contents of Ce3+ and Fe3+ can be obtained on the sulfated catalysts, especially for the SFC catalyst. Meanwhile, different sulfation strategies will progressively enhance the redox ability and amounts of strong acid sites, which will contribute to broadening the operating temperature window for the NH3-SCR reaction. Additionally, different sulfation methods do not change the reaction pathway of catalysts. However, the adsorption of ad-NH3 species and reactivity of ad-NOx species are significantly changed. These lead to the reaction pathway shifts to E-R direct over the SFC and the promotion of E-R and L-H mechanisms over the FCS catalyst.

Catalytic performance and reaction mechanisms of NO removal with NH3 at low and medium temperatures on Mn-W-Sb modified siderite catalysts.

Iron-based catalysts have been explored for selective catalytic reduction (SCR) of NO due to environmentally benign characters and good SCR activity. Mn-W-Sb modified siderite catalysts were prepared by impregnation method based on siderite ore, and SCR performance of the catalysts was investigated. The catalysts were analyzed by X-ray diffraction, H2-temperature-programmed reduction, Brunauer-Emmett-Teller, Thermogravimetry-derivative thermogravimetry and in-situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified siderite catalysts calcined at 450°C mainly consist of Fe2O3, and added Mn, W and Sb species are amorphous. 3Mn-5W-1.5Sb-siderite catalyst has a wide temperature window of 180-360°C and good N2 selectivity at low temperatures. In-situ DRIFTS results show NH4+, coordinated NH3, NH2, NO3- species (bidentate), NO2- species (nitro, nitro-nitrito, monodentate), and adsorbed NO2 can be discovered on the surface of Mn-W-Sb modified siderite catalysts, and doping of Mn will enhance adsorbed NO2 formation by synergistic catalysis with Fe3+. In addition, the addition of Sb can inhibit sulfates formation on the surface of the catalyst in the presence of SO2 and H2O. Time-dependent in-situ DRIFTS studies also indicate that both of Lewis and Brønsted acid sites play a role in SCR of NO by ammonia at low temperatures. The mechanism of NO removal on the 3Mn-5W-1.5Sb-siderite catalyst can be discovered as a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms with three reaction pathways. The mechanism of NO, oxidized by synergistic catalysis of Fe3+ and Mn4+/3+ to form NO2 among three pathways, reveals the reason of high NOx conversion of the catalyst at medium and low temperatures.

Effect of CaCO3 on catalytic activity of Fe-Ce/Ti catalysts for NH3-SCR reaction.

In the present work, fresh and Ca poisoned Fe-Ce/Ti catalysts were prepared and used for the NH3-SCR reaction to investigate the effect of Ca doping on the catalytic activity of catalysts. And these catalysts were characterized by BET, XRD, Raman, UV-vis DRS, XPS, H2-TPR, and NH3-TPD techniques. The obtained results demonstrate that Ca doping could lead to an obvious decrease in the catalytic activity of catalysts. The reasons for this may be due to the smaller specific surface area and pore volume, the decreased ratio of Fe3+/Fe2+ and Ce3+/Ce4+, as well as the reduced redox ability and surface acidity.

Superior activity of iron-manganese supported on kaolin for NO abatement at low temperature.

A series of Fe-Mn catalysts was prepared using different supports (kaolin, diatomite, and alumina) and used for NO abatement via low-temperature NH3-selective catalytic reduction (SCR). The results showed that 12Fe-10Mn/Kaolin (with the concentration of Fe and Mn 12 and 10wt.%, respectively) exhibited the highest activity, and more than 95.8% NO conversion could be obtained within the wide temperature range of 120-300°C. The properties of the catalysts were characterized by inductively coupled plasma-atomic emission spectrometry (ICP-AES), thermogravimetry (TG), Brunner-Emmet-Teller (BET) measurements, X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), NH3-temperature programmed desorption (NH3-TPD), X-ray photoelectron spectroscopy (XPS), scanning electron microprobe (SEM) and energy dispersive spectroscopy (EDS) techniques. The support effects resulted in significant differences in the components and structures of catalysts. The 12Fe-10Mn/Kaolin catalyst exhibited better dispersion of active species, optimum low-temperature reduction behavior, the largest amount of normalized Brønsted acid sites, and the highest Mn4+/Mn and Fe3+/(Fe3++Fe2+), all of which may be major reasons for its superior catalytic activity.

Promoted dispersion and uniformity of active species on Fe-Ce-Al catalysts for efficient NO abatement.

Fe-Ce-Al catalysts were synthesized by the co-precipitation method (labeled as Fe-Ce-Al-P), co-impregnation method (Fe-Ce-Al-I), and direct mixing method (Fe-Ce-Al-M), respectively, and used for effective removal of NO. The synthesized catalysts were characterized by many methods including N2 physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), high-resolution transmission electron microscopy (HR-TEM), and energy dispersive spectroscopy (EDS) mapping. The results show that the synthesis methods greatly influence the catalytic performance of catalysts. The Fe-Ce-Al-P catalyst prepared by the co-precipitation method yields the highest catalytic performance, while the Fe-Ce-Al-I and Fe-Ce-Al-M catalysts exhibit relatively low catalytic activity. The co-precipitation method can promote the accumulation and dispersion of more surface active species on the catalyst surface, and provide smaller particle size of active species and generate more uniform particle size distribution, while these characteristics can't be obtained by the co-impregnation method and direct mixing method. Moreover, the co-precipitation method could produce the highest surface area and enhanced redox ability and surface acidity of the catalyst, which resulted from the high dispersion and uniform distribution of surface active species. These may be the key factors to the superior catalytic performance of the Fe-Ce-Al-P catalyst.

Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3.

Fe2O3 particle catalysts were experimentally studied in the low temperature selective catalytic reduction (SCR) of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe2O3 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270 degrees C, and more than 95% NO conversion was obtained at 180 degrees C when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and O2 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180 degrees C. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.

[Experimental studies on low-temperature selective catalytic reduction of NO on magnetic iron-based catalysts].

Low-temperature selective catalytic reduction (SCR) of NO is a new technique needing urgent development in flue gas cleaning. Elementary studies were done about selective catalytic reduction of NO from flue gas on magnetic iron oxides with ammonia at low and medium temperatures in a fluidized bed, such as Fe3O4 and gamma-Fe2O3. Magnetic field effects for NO removal on gamma-Fe2O3 were also researched with low assisted magnetic fileds. X-ray diffraction spectroscopy was used to identify and characterize the iron oxides catalysts. Results show that gamma-Fe2O3 is active in SCR at low temperatures, and Fe3O4 is apparently less active in SCR than gamma-Fe2O3, but Fe2O3 is also active in ammonia oxidation by O2 above 25 degrees C. Therefore, the optimal catalytic temperature zone in SCR on gamma-Fe2O3 includes 250 degrees C and adjacent temperature zone below it. Furthermore, a better NO conversion, which is 90%, is obtained at 250 degrees C on the gamma-Fe2O3 particle catalyst. In addition, chemisorption of NO on gamma-Fe2O3 is accelerated by assisted magnetic fields at 150-290 degrees C, thus the NO conversion is improved and higher NO removal efficiency of 95% is obtained at 250 degrees C. But the efficiency of NO removal decreases above 290 degrees C with the magnetic field. It is concluded that gamma-FeO3 catalyst is fit to be used in low-temperature SCR of NO with ammonia at 200-250 degrees C, which may suppress oxidation of ammonia and take advantage of positive effects by external magnetic fields.

A novel semidry flue gas desulfurization process with the magnetically fluidized bed reactor.

The magnetically fluidized bed (MFB) was used as the reactor in a novel semidry flue gas desulfurization (FGD) process to achieve high desulfurization efficiency. Experiments in a laboratory-scale apparatus were conducted to reveal the effects of approach to adiabatic saturation temperature, Ca/S molar ratio and applied magnetic field intensity on SO(2) removal. Results showed that SO(2) removal efficiency can be obviously enhanced by decreasing approach to adiabatic saturation temperature, increasing Ca/S molar ratio, or increasing applied magnetic field intensity. At a magnetic field intensity of 300Oe and a Ca/S molar ratio of 1.0, the desulfurization efficiency (excluding desulfurization efficiency in the fabric filter) was over 80%, while spent sorbent appeared in the form of dry powder. With the SEM, XRD and EDX research, it can be found that the increase of DC magnetic field intensity can make the surface morphology on the surface of the ferromagnetic particles loose and enhance the oxidation of S(IV), hence reducing the liquid phase mass transfer resistance of the slurry droplets and increasing desulfurization reaction rate, respectively. Therefore, the desulfurization efficiency increased obviously with the increase of DC field intensity.