CeO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> Mixed Oxides for the Selective Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> by NH<Subscript>3</Subscript> Over a Wide Temperature Range

Abstract  

A series of cerium-tungsten oxide catalysts was prepared by the co-precipitation method and was evaluated for the selective catalytic reduction of NO _x by ammonia (NH₃-SCR) over a wide temperature range. These catalysts were characterized by BET, XRD, XPS and H₂-TPR analyses. The experimental studies demonstrated that, among cerium-tungsten oxides, CeO₂–WO₃ with a Ce/W molar ratio of 3/2 exhibited the best activity toward NH₃-SCR reactions, N₂ selectivity and SO₂ durability over a broad temperature range of 175–500 °C at a space velocity of 47,000 h⁻¹. The strong interaction between Ce and W could be the main factor leading to the high activity of the CeO₂–WO₃ mixed oxide catalyst.     

Investigating the Influence of Fe Speciation on N<Subscript>2</Subscript>O Decomposition Over Fe–ZSM-5 Catalysts

The influence of Fe speciation on the decomposition rates of N₂O over Fe–ZSM-5 catalysts prepared by Chemical Vapour Impregnation were investigated. Various weight loadings of Fe–ZSM-5 catalysts were prepared from the parent zeolite H-ZSM-5 with a Si:Al ratio of 23 or 30. The effect of Si:Al ratio and Fe weight loading was initially investigated before focussing on a single weight loading and the effects of acid washing on catalyst activity and iron speciation. UV/Vis spectroscopy, surface area analysis, XPS and ICP-OES of the acid washed catalysts indicated a reduction of ca. 60% of Fe loading when compared to the parent catalyst with a 0.4 wt% Fe loading. The TOF of N₂O decomposition at 600 °C improved to 3.99?×?10³ s^?1 over the acid washed catalyst which had a weight loading of 0.16%, in contrast, the parent catalyst had a TOF of 1.60?×?10³ s^?1. Propane was added to the gas stream to act as a reductant and remove any inhibiting oxygen species that remain on the surface of the catalyst. Comparison of catalysts with relatively high and low Fe loadings achieved comparable levels of N₂O decomposition when propane is present. When only N₂O is present, low metal loading Fe–ZSM-5 catalysts are not capable of achieving high conversions due to the low proximity of active framework Fe³⁺ ions and extra-framework ɑ-Fe species, which limits oxygen desorption. Acid washing extracts Fe from these active sites and deposits it on the surface of the catalyst as Fe_xO_y, leading to a drop in activity. The Fe species present in the catalyst were identified using UV/Vis spectroscopy and speculate on the active species. We consider high loadings of Fe do not lead to an active catalyst when propane is present due to the formation of Fe_xO_y nanoparticles and clusters during catalyst preparation. These are inactive species which lead to a decrease in overall efficiency of the Fe ions and consequentially a lower TOF.     

Hydrodechlorination of CCl<Subscript>4</Subscript> on Pt–Au/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

A series of Pt/Al₂O₃ catalysts were prepared by the impregnation method and were characterized by TEM, XRD, H₂ and CO chemisorptions, and investigated in the hydrodechlorination of tetrachloromethane. Three Pt-rich, Pt–Au/Al₂O₃ catalysts (Pt₁₀₀, Pt₉₅Au₅ and Pt₉₀Au₁₀) showed a similar metal particle size (~2.5–2.7 nm), so observed changes in the catalytic behavior are ascribed to alloying effect, especially because a considerable degree of Pt–Au mixing was achieved in the bimetallic samples. It appeared that by introducing very small amount of gold (10 at.%) to platinum, the catalytic activity is increased. It is argued that the occurrence of this moderate synergistic effect is associated with a decreased tendency of surface chloriding when platinum is alloyed with gold. Zbigniew Kowalczyk—deceased.     

Study on flame structures and emissions of CO and NO in Various CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript>–O<Subscript>2</Subscript>/N<Subscript>2</Subscript> counterflow premixed flames

An oxygen-diluted partially premixed/oxygen-enriched supplemental combustion (ODPP/OESC) counterflow flame is studied in this paper. Flame images are obtained through experiments and numerical simulations with the GRI-Mech 3.0 chemistry. The oxygen dilution effects are revealed by comparing the flame structures and emissions with those of a premixed flame and partially premixed flame (PPF) at the same equivalence ratio (?_Σ = 0.95 and ? _f = 1.4). The results show that both PPF and ODPP/OESC flames have distinct double flame structures; however, the location of the premixed combustion zone and the distance between premixed/nonpremixed combustion zone are significantly different for these two cases. For the ODPP/OESC flame, the temperature in the premixed combustion zone is lower and the premixed zone itself is located farther downstream from the fuel nozzle, which leads to reduction of NO and CO emissions, as compared to those of the PPF. Therefore, by adjusting the distribution of the oxygen concentration in the premixed and nonpremixed combustion zones, the ODPP/OESC can effectively balance the chemical reaction rate in the entire combustion zone and, consequently, reduce emissions.     

Enhancement of the Activities of γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Methane-SCR of NO by Treatment with NH<Subscript>3</Subscript>

Abstract  

The precursor particles for γ-Ga₂O₃–Al₂O₃ solid solutions were prepared by the coprecipitation method from aqueous solutions of Ga(NO₃)₃ and Al(NO₃)₃ with (NH₄)₂CO₃ as a precipitant. The γ-Ga₂O₃–Al₂O₃ solid solutions were obtained by calcination of the precursor at 700 °C. In this paper, the performance of the catalysts treated with NH₃ was investigated for the selective catalytic reduction (SCR) of NO with methane as a reducing agent, and it was found that γ-Ga₂O₃–Al₂O₃ catalysts treated with NH₃ and subsequently annealed in air showed higher activities than the γ-Ga₂O₃–Al₂O₃ catalysts without NH₃ treatment. NH₃ treatment of the catalyst caused partial rearrangement of Ga³⁺ and Al³⁺ ions and increased the population of tetrahedral Ga³⁺ ions in the defective spinel structure.     

Selective Catalytic Reduction of NO x Over Nano-Sized Gold Catalysts Supported on Alumina and Titania and Over Bimetallic Gold–Silver Catalysts Supported on Alumina

The reduction of NO with octane under lean conditions was examined over gold supported on alumina and titania and over alumina supported bimetallic gold–silver catalysts. The silver loading was either 1.2 or 1.9 wt% whereas 0.3, 1 or 5 wt% gold was used. The catalysts were characterized by means of EDXS, N₂-adsortion, UV–Vis and TEM to correlate recorded results with different preparation methods. UV–Vis measurements indicated that gold was present in the form of fine Au particles, single Au ions and small (Au)_n ^δ+ clusters on the catalysts and silver was mainly present in the form of single Ag ions. The highest NO to N₂ reduction activity was recorded over the 0.3Au–Al₂O₃ catalyst. The Au–TiO₂ catalysts did not result in significant NO to N₂ reduction.     

Hydroisomerization of Benzene-Containing Gasoline Fraction on Pt/B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/WO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

The effect of the hydroisomerization conditions of the benzene-containing fraction of catalytic reforming gasoline on the yield and composition of products is studied on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts. These catalysts allow benzene to be completely removed from the raw material. At the same time, the greatest yields of liquid products are obtained with minimal losses of the octane number at 2 MPa, a mass feedstock hourly space velocity (MFHSV) of 2 h^?1, and 325°C: 96.3 and 95.4 wt % on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts, respectively. The activity of the catalysts is maintained for 100 h during their operation.     

Physicochemical Properties of Nanosized Powders of the LaPO<Subscript>4</Subscript>–DyPO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O System

Nanosized La_1–xDy_xPO₄ · nH₂O powders are synthesized by the sol-gel method using direct and reverse precipitation. The formation of a continuous series of hexagonal solid solutions based on LaPO₄ · nH₂O is confirmed by the XRD and DSC/TG methods. A continuous series of monoclinic solid solutions based on LaPO4 is formed at temperatures higher than 600°C. A reflex corresponding to a tetragonal form of DyPO₄ is formed during the calcination of DyPO₄ powder at 850°C. Two types of solid solutions are observed at temperatures of 1000–1200°C, namely, monoclinic solutions based on LaPO₄ (to x ≈ 0.7) and tetragonal solutions based on DyPO₄ (0.90 ≤ x ≤ 1.0). The results are compared depending on the methods of nanopowder synthesis.     

Physicomechanical properties of refractory Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C materials with ACPC

A study has been made on the effects of the amount of silicon nitride and graphite on the physicomechanical properties of Al₂O₃–Si₃N₄–C composites for lining purposes. Adding 2.5–5.0 wt.% silicon nitride and 0.5 wt.% reactive alumina improves the properties, raises their apparent density, and increases the mechanical strength, while reducing the open porosity. Optimized compositions have been determined for refractory materials of Al₂O₃–Si₃N₄–C composition, and it has been found that to attain the higher values of physicomechanical properties the amount of graphite should constitute 5–10 wt.%.     

Facile Synthesis of Ag–γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Superior Nanocomposite for Catalytic Reduction of Nitroaromatic Compounds and Catalytic Degradation of Methyl Orange

A facile synthetic route for preparing silver-doped maghemite (Ag–γ-Fe₂O₃) nanocomposite via a modified co-precipitation method was developed. The prepared magnetic nanocomposite was characterized by means of thermal analysis, transmission electron microscope, X-Ray diffraction, vibrating sample magnetometer and Fourier transform infrared techniques. The characterization results showed that the prepared Ag–γ-Fe₂O₃ nanocomposite is nanocrystalline and 6–8 nm in size with superparamagnetic behavior. The synthesized Ag–γ-Fe₂O₃ nanocomposite showed exceptional catalytic activities towards reduction of nitroaromatic compounds with specific activities parameters of 1441.7 and 904.2 s^??1 g_Ag^?1 for both 4-nitrophenol and 2-nitroaniline, respectively. Besides, it shows a superior activity for catalytic degradation of methyl orange. All the three catalytic reactions were carried out in aqueous medium at room temperature and in the presence of reducing agent NaBH₄. The magnetic behavior of the synthesized Ag–γ-Fe₂O₃ enables the ease of separation of the nanocomposite from the reaction medium for further reuse.

Graphical Abstract

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