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1.
The monooxides copper, manganese, molybdenum and chromium catalysts supported on MgF 2 were tested in NO decomposition and reduction by propene. The effect of the oxides content, time on stream and O 2 concentration in reaction mixture during NO reduction on their catalytic activity was investigated. All the catalysts showed the optimum active phase concentration corresponding to 2–4 wt.% of the metal. For the best copper catalyst an effect of introduction of another oxide (manganese or chromium oxide) on the catalytic performance was studied. The double copper-manganese oxide sample containing 2 wt.% Cu and 4 wt.% Mn was proved to ensure the best catalytic performance. 相似文献
2.
The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O 2. Among the Ba catalysts supported on single-component metal oxides, Ba/Co 3O 4 and Ba/CeO 2 showed high NO decomposition activities, while Ba/Al 2O 3, Ba/SiO 2, and Ba/TiO 2 exhibited quite low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found that the activities were significantly enhanced using Ce–Mn mixed oxides as support materials. XRD results indicated the formation of CeO 2–MnO x solid solutions with the cubic fluorite structure. O 2-TPD of the CeO 2–MnO x solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO 2–MnO x solid solutions were larger than those of pure CeO 2 and Mn 2O 3. These effects caused by the addition of Mn are responsible for the enhanced activities of the Ba catalysts supported on Ce–Mn mixed oxides. 相似文献
3.
The reaction pathways of N 2 and N 2O formation in the direct decomposition and reduction of NO by NH 3 were investigated over a polycrystalline Pt catalyst between 323 and 973 K by transient experiments using the temporal analysis of products (TAP-2) reactor. The interaction between nitric oxide and ammonia was studied in the sequential pulse mode applying 15NO. Differently labelled nitrogen and nitrous oxide molecules were detected. In both, direct NO decomposition and NH 3–NO interaction, N 2O formation was most marked between 573 and 673 K, whereas N 2 formation dominated at higher temperatures. An unusual interruption of nitrogen formation in the 15NO pulse at 473 K was caused by an inhibiting effect of adsorbed NO species. The detailed analysis of the product distribution at this temperature clearly indicates different reaction pathways leading to the product formation. Nitrogen formation occurs via recombination of nitrogen atoms formed by dissociation of nitric oxide or/and complete dehydrogenation of ammonia. N 2O is formed via recombination of adsorbed NO molecules. Additionally, both products are formed via interactions between adsorbed ammonia fragments and nitric oxide. 相似文献
5.
Various spinel-type catalysts AB 2O 4 (where A = Mg, Ca, Mn, Co, Ni, Cu, Cr, Fe, Zn and B = Cr, Fe, Co) were prepared and characterized by XRD, BET, TEM and FESEM-EDS. The performance of these catalysts towards the decomposition of N 2O to N 2 and O 2 was evaluated in a temperature programmed reaction (TPR) apparatus in the absence and the presence of oxygen. Spinel-type oxides containing Co at the B site were found to provide the best activity. The half conversion temperature of nitrous oxide over the MgCo 2O 4 catalyst was 440 °C and 470 °C in the absence and presence of oxygen, respectively (GHSV = 80,000 h −1). On the grounds of temperature programmed oxygen desorption (TPD) analyses as well as of reactive runs, the prevalent activity of the MgCo2O4 catalyst could be explained by its higher concentration of suprafacial, weakly chemisorbed oxygen species, whose related vacancies contribute actively to nitrous oxide catalytic decomposition. This indicates the way for the development of new, more active catalysts, possibly capable of delivering at low temperatures amounts of these oxygen species even higher than those characteristic of MgCo2O4. 相似文献
6.
The decomposition of N 2O, and the catalytic reduction by NH 3 of N 2O and N 2O + NO, have been studied on Fe-BEA, -ZSM-5 and -FER catalysts. These catalysts were prepared by classical ion exchange and characterized by TPR after various activation treatments. Fe-FER is the most active material in the catalytic decomposition because “oxo-species” reducible at low temperature, appearing upon interaction of Fe II-zeolite with N 2O (-oxygen), are formed in largest amounts with this material. The decomposition of N 2O is promoted by addition of NH 3, and even more with NH 3 + NO in the case of Fe-FER and -BEA. It is proposed that the NO-promoted reduction of N 2O originated from the fast surface reaction between -oxygen O * and NO * to yield NO 2*, which in turn reacts immediately with NH 3. 相似文献
7.
Dispersing La 2O 3 on δ- or γ-Al 2O 3 significantly enhances the rate of NO reduction by CH 4 in 1% O 2, compared to unsupported La 2O 3. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La 2O 3 precursor used, the pretreatment, and the La 2O 3 loading. The most active family of catalysts consisted of La 2O 3 on γ-Al 2O 3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m 2) occurred between the addition of one and two theoretical monolayers of La 2O 3 on the γ-Al 2O 3 surface. The best catalyst, 40% La 2O 3/γ-Al 2O 3, had a turnover frequency at 700°C of 0.05 s −1, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La 2O 3/Al 2O 3 catalysts exhibited stable activity under high conversion conditions as well as high CH 4 selectivity (CH 4 + NO vs. CH 4 + O 2). The addition of Sr to a 20% La 2O 3/γ-Al 2O 3 sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO =4 to the latter Sr-promoted La 2O 3/Al 2O 3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La 2O 3. Dispersing La 2O 3 on SiO 2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La 2O 3. This is presumably due to water sensitivity and silicate formation. The La 2O 3/Al 2O 3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications. 相似文献
8.
A mechanistic scheme of N 2O and N 2 formation in the selective catalytic reduction of NO with NH 3 over a Ag/Al 2O 3 catalyst in the presence and absence of H 2 and O 2 was developed by applying a combination of different techniques: transient experiments with isotopic tracers in the temporal analysis of products reactor, HRTEM, in situ UV/vis and in situ FTIR spectroscopy. Based on the results of transient isotopic analysis and in situ IR experiments, it is suggested that N 2 and N 2O are formed via direct or oxygen-induced decomposition of surface NH 2NO species. These intermediates originate from NO and surface NH 2 fragments. The latter NH 2 species are formed upon stripping of hydrogen from ammonia by adsorbed oxygen species, which are produced over reduced silver species from NO, N 2O and O 2. The latter is the dominant supplier of active oxygen species. Lattice oxygen in oxidized AgO x particles is less active than adsorbed oxygen species particularly below 623 K. The previously reported significant diminishing of N 2O production in the presence of H 2 is ascribed to hydrogen-induced generation of metallic silver sites, which are responsible for N 2O decomposition. 相似文献
9.
This study reports the potential interest of LaCoO 3 in the catalytic decomposition of N 2O from nitric acid plants. Typically, the exhaust gas contains NO, water and O 2 which usually induce strong inhibiting effects depending on the surface properties of the solids particularly the surface mobility of oxygen from LaCoO 3. Different preparation methods have been implemented, involving citrate route, reactive grinding and the use of templates, which lead to different structural and textural properties examined by X-ray diffraction, transmission electron microscopy and N 2 physisorption. EDX analysis and XPS measurements also revealed that different surface composition may alter subsequent interactions between the surface and the reactants and related catalytic performances. LaCoO 3 prepared by reactive grinding was found to be the most active catalyst due to a high specific surface area but the presence of Fe and Zn impurities inherent to the preparation method were suggested to interfere on the catalytic performances. 相似文献
10.
A detailed temperature-programmed desorption (TPD) study on NO and O 2 saturated Cu-ZSM-5 at different temperatures (300–723 K) has been performed. In the temperature range 373–723 K, the evolution of O 2 and NO 2 accompanying the desorption of NO from NO saturated Cu-ZSM-5 suggested the formation of nitrite/nitrate species. The amount of O 2 absorbed was very much lower than that of NO. The desorption profile of O 2 after contacting Cu-ZSM-5 with O 2 at 623 K showed a low temperature peak (369K) confirming the spontaneous ability of O 2 desorption from copper zeolite. Moreover, successive saturation cycles of NO followed by O 2 and vice versa have been performed at various temperatures (298–623 K) to understand the modifications which the adsorption sites undergo when the two molecules NO and O 2 are available together for adsorption on the catalyst sites. After each saturation cycle, a TPD profile was recorded following the evolution of NO, O 2 and other NO x species. The competitive adsorption experiments revealed that, at 623 K, NO was not able to successfully compete with O 2 for the adsorption sites, therefore the adsorption of NO at 623 K on O 2 saturated catalyst was not completely restored. On the basis of the experimental work, an overall adsorption reaction scheme of NO on Cu-ZSM-5 was proposed 相似文献
11.
Both NO decomposition and NO reduction by CH 4 over 4%Sr/La 2O 3 in the absence and presence of O 2 were examined between 773 and 973 K, and N 2O decomposition was also studied. The presence of CH 4 greatly increased the conversion of NO to N 2 and this activity was further enhanced by co-fed O 2. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH 4 in the absence of O 2, and reduction with 1% O 2 in the feed were 8.3·10 −4, 4.6·10 −3, and 1.3·10 −2 μmol N 2/s m 2, respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N 2 formation by decomposition was inhibited by O 2 in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH 4 continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O 2 with equal activation energies of 26 kcal/mol. The addition of O 2 increased the reaction order in CH 4 at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O 2 was 0.26 up to 0.5% O 2 during which time the CH 4 concentration was not decreased significantly. N 2O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10 −4 μmol N 2/s m 2 at 623 K and 1220 ppm N 2O and an activation energy of 24 kcal/mol. The addition of CH 4 inhibits this decomposition reaction. Finally, the use of either CO or H 2 as the reductant (no O 2) produced specific activities at 773 K that were almost 5 times greater than that with CH 4 and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H 2 to reduce NO to N 2 over these REO catalysts. 相似文献
12.
A series of CeO 2 promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N 2O). Addition of CeO 2 to Co 3O 4 led to an improvement in the catalytic activity for N 2O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N 2O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O 2, H 2O or NO. Methods of XRD, FE-SEM, BET, XPS, H 2-TPR and O 2-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO 2 could increase the surface area of Co 3O 4, and then improve the reduction of Co 3+ to Co 2+ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N 2O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO 2, are responsible for the enhancement of catalytic activity of Co 3O 4. 相似文献
13.
NO decomposition at 673 K as a function of contact times over a V-O-W/Ti(Sn)O 2 catalyst obtained by sol–gel method and pretreated at 673 K in helium stream was investigated and compared with that over a Cu-ZSM-5 catalyst. Feed containing 4% NO in a helium stream was used in both the cases. The V-O-W/Ti(Sn)O2 catalyst showed higher activity as well as higher selectivity to dinitrogen than the Cu-ZSM-5 catalyst over the whole range of used contact times (0.375–15 g s cm−3). The highest activity of the V-O-W/Ti(Sn)O2 catalyst, especially at higher normalised contact times (τ/τmax > 0.25), was shown to result from vanadia-like surface layer formation with high tungsten content. It was also shown that the decrease in activity as contact time decreased is connected with tungsta monolayer formation on the V-O-W hybrid crystallites composed of tungsta, V-W oxide bronze and vanadia. 相似文献
14.
以等体积浸渍法制备γ-Al_2O_3负载的Co、Cu、Ce和Fe氧化物催化剂,利用正交试验设计实验条件,采用XRD、BET和H_2-TPR等对催化剂进行表征,并考察活性组分对催化剂催化分解N_2O活性的影响。结果表明,催化剂具有尖晶石结构,其BET比表面积随着金属氧化物负载量增加而降低。催化剂中铜的氧化物可以降低还原峰温度,进而明显提高催化活性,Co和Fe的加入对活性有一定的提高,Ce对催化活性没有明显影响。 相似文献
15.
This work investigates the electric field effect on nitrogen oxide (NO) pollutant formation and emission composition of premixed flames in order to provide better insight on the mechanism of controlling the combustion process by electro-physical means. The present study aims to investigate experimentally the effect of radial DC electric field on premixed laminar methane flame. The electric field effect on flame shape, emission composition and NO emission index of flame is investigated experimentally under the action of direct-current electric field under varying equivalence ratio and level of oxygen enrichment. The results show that ionic wind effects cause the distortion in flame shape. The ionic wind effects diminish with increasing flow rate and level of oxygen enrichment. Minimal effects on NO are measured for flames under the influence of electric field and vanished as the level of oxygen enrichment is increased. This was well supported by the temperature profile measurement in the post flame gas showing no field-induced modification also. It seemed that the action of an electric field on a flame with a geometry that remains practically undeformed produces very minimal effect on pollutant emission. 相似文献
16.
Direct decomposition of nitrous oxide (N 2O) on K-doped Co 3O 4 catalysts was examined. The K-doped Co 3O 4 catalyst showed a high activity even in the presence of water. In the durability test of the K-doped Co 3O 4 catalyst, the activity was maintained at least for 12 h. It was found that the activity of the K-doped Co 3O 4 catalyst strongly depended on the amount of K in the catalyst. In order to reveal the role of the K component on the catalytic activity, the catalyst was characterized by XRD, XPS, TPR and TPD. The results suggested that regeneration of the Co 2+ species from the Co 3+ species formed by oxidation of Co 2+ with the oxygen atoms formed by N 2O decomposition was promoted by the addition of K to the Co 3O 4 catalyst. 相似文献
17.
Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La 0.87Sr 0.13Mn 0.2Ni 0.8O 3−δ, La 0.66Sr 0.34Ni 0.3Co 0.7O 3−δ and La 0.8Sr 0.2Cu 0.15Fe 0.85O 3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO 2, H 2O and CH 4 on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H 2O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO 2 and H 2O inhibit the NO decomposition, but inhibition by CO 2 is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO 2 and H 2O over the three perovskites were determined. Addition of methane to the feed (NO/CH 4=4) increases conversion of NO to N 2 about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane. 相似文献
18.
The decomposition of nitrous oxide to nitrogen and oxygen using a series of monolithic (ceria-alumina washcoated cordierite) supported transition metal (Cu, Fe, Co, Ni, Mn) and noble metal (Ir, Rh) oxide catalysts has been studied using gas chromatography. The effect of combining a transition metal with a noble metal has also been investigated. A synergetic effect was observed between transition metal and noble metal oxides in the presence of a small amount of water for some of the catalysts. The synergy between Fe-Ir and Ni-Ir was also verified under dry conditions. X-ray photoelectron spectroscopic measurements on these catalysts indicate that Fe, Rh and Ir are present predominantly as Fe 2O 3, RhO 2 and IrO 2, while significant amounts of Co and Ni ions may migrate inside the support to form cobalt and nickel aluminate. Only the Fe-Ir catalyst showed a significant interaction between the noble metal and the transition metal. The effect of water, oxygen and carbon monoxide on the catalytic behaviour of the five most active catalysts (Ni-Ir, Ni-Rh, Fe-Ir, Co-Ir, Ir) has also been investigated. Oxygen and water were found to inhibit the catalytic activity, although the extent of oxygen inhibition is limited, presumably due to the presence of ceria in the monolith washcoat support. Conversely, carbon monoxide greatly enhances catalytic activity. 相似文献
19.
In situ X-ray diffraction (XRD) and quasi in situ X-ray photoelectron spectroscopy (XPS) measurements were complementary used to investigate structural and surface modifications of a palladium-supported on LaCoO 3 perovskite catalyst under various controlled atmospheres, particularly during the reduction of NO by hydrogen under lean conditions, in the presence of a large excess of oxygen. An extensive reduction of the perovskite was evidenced during the pre-activation thermal treatment of the palladium-supported catalyst under hydrogen at 773 K leading to the formation of Pd particles in contact with Co0 and La2O3. In the presence of an excess of oxygen, the catalyst structure changes during the reaction. The reduced solid is progressively transformed into LaCoO3 in the range of 873–1173 K. However, such a bulk transformation probably occurs at lower temperatures at the surface of the solid according to XPS analyses. At the same time, the binding energy (BE) level of the Pd 3d5/2 photopeak increases up to 337.5 eV which reveals the stabilisation of oxidic palladium species in a different chemical environment than that corresponding to PdO. Such changes induced different catalytic properties of the catalyst during the reduction of NO by H2. 相似文献
20.
Polycrystalline samples of manganese substituted lead zirconium titanate (PZMT) with general formula Pb(Zr 0.65−xMn xTi 0.35)O 3 ceramics have been synthesised by high temperature solid state reaction technique. X-ray diffraction (XRD) patterns were recorded at room temperature to study the crystal structure employing Rietveld technique. All the patterns could be refined to R3c space group with rhombohedral symmetry. Bond lengths and angles have been calculated from refined parameters. Microstructural properties of the materials were analysed by scanning electron microscope (SEM) and compositional analysis were carried out by energy dispersive spectrum (EDS) measurements. All the materials exhibit ferroelectric to paraelectric transition. The Curie temperature ( Tc) increases with the Mn concentration. We have observed that dielectric constant decreases and AC conductivity increases with the frequency. The correlation between lattice parameters and Tc for the present samples has been observed. 相似文献
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