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1.
Hong He  Changbin Zhang  Yunbo Yu 《Catalysis Today》2004,90(3-4):191-materials
The selective catalytic reduction (SCR) of NO by C3H6 in excess oxygen was evaluated and compared over Ag/Al2O3 and Cu/Al2O3 catalysts. Ag/Al2O3 showed a high activity for NO reduction. However, Cu/Al2O3 showed a high activity for C3H6 oxidation. The partial oxidation of C3H6 gave surface enolic species and acetate species on the Ag/Al2O3, but only an acetate species was clearly observed on the Cu/Al2O3. The enolic species is a more active intermediate towards NO + O2 to yield—NCO species than the acetate species on the Ag/Al2O3 catalyst. The Ag and Cu metal loadings and phase changes on Al2O3 support can affect the activity and selectivity of Ag/Al2O3 and Cu/Al2O3 catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al2O3 catalyst for NO reduction is higher than that of the Cu/Al2O3 catalyst.  相似文献   

2.
The effect of the nature and distribution of VOx species over amorphous and well-ordered (MCM-41) SiO2 as well as over γ-Al2O3 on their performance in the oxidative dehydrogenation of propane with O2 and N2O was studied using in situ UV–vis, ex situ XRD and H2-TPR analysis in combination with steady-state catalytic tests. As compared to the alumina support, differently structured SiO2 supports stabilise highly dispersed surface VOx species at higher vanadium loading. These species are more selective over the latter materials than over V/γ-Al2O3 catalysts. This finding was explained by the difference in acidic properties of silica- and alumina-based supports. C3H6 selectivity over V/γ-Al2O3 materials is improved by covering the support fully with well-dispersed VOx species. Additionally, C3H6 selectivity over all materials studied can be tuned by using an alternative oxidising agent (N2O). The improving effect of N2O on C3H6 selectivity is related to the lower ability of N2O for catalyst reoxidation resulting in an increase in the degree of catalyst reduction, i.e. spatial separation of active lattice oxygen in surface VOx species. Such separation favours selective oxidation over COx formation.  相似文献   

3.
The decomposition of different hydrocarbons (CH4, C2H6, C2H4, C2H2, C3H8, and C3H6) over Ni (5 wt.%)/SiO2 catalysts was carried out. The initial rates of decomposition of the hydrocarbons, the kinetic curves of the decomposition and the kinetic curves of the hydrogenation of deposited carbon into methane depended on the types of hydrocarbons. In addition, the catalytic life of the Ni/SiO2 catalyst was also dependent on the types of hydrocarbons, i.e. the life was longer according to the order, alkanes>alkenesacetylene.

The carbons deposited on the catalyst were characterized by SEM and Raman spectroscopy. The appearances of the deposited carbons were different among alkanes, alkenes, and acetylene, i.e. a zigzag fiber structure from methane, and a rolled fiber structure from alkenes and acetylene. From Raman spectra of the deposited carbons, it was found that the degree of graphitization of deposited carbon was higher in the order, alkanes>alkenes>acetylene. These results suggest that the mechanism of decomposition of hydrocarbons and the growth mechanism of carbon fibers on the catalyst were different among alkanes, alkenes and acetylene.  相似文献   


4.
The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al2O3 catalysts on the surface properties and reactivity for NO reduction by C3H6 in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al2O3 catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al2O3 and 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalysts calcined at 1073 K possess a CuAl2O4 phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C3H6 shows that the CuAl2O4 is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K, although these catalysts possess the same CuAl2O4 phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K is attributed to the formation of less active CuAl2O4 phase with high aggregation and preferential promotion of C3H6 combustion to COx by MnO2. The engine dynamometer test for NO reduction shows that the C3H6 is a more effective reducing agent for NO reduction than the C2H5OH. The maximum reactivity for NO reduction by C3H6 is reached when the NO/C3H6 ratio is one.  相似文献   

5.
A series of CoOx/Al2O3 catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C3H8. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co3O4 crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoOx/Al2O3 catalyst shows high activity in SCR of NO by C3H8 (100% conversion of NO at 723 K, GHSV: 10,000 h−1). The activity of the selective catalytic reduction of NO by C3H8 increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl2O4 crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co3O4 crystallites catalyze the combustion of C3H8 only.  相似文献   

6.
This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO2 with C2H4 as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C2H4/SO2, and pretreatment are all important factors affecting catalyst activity. Fe2O3/γ-Al2O3 was found to be the most active catalyst among six γ-Al2O3-supported metal oxide catalysts tested. With Fe2O3 as the active species, of the supports tested, CeO2 is the most suitable one. Using this Fe2O3/CeO2 catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C2H4/SO2 is 1:1, and the catalyst presulfidized by H2+H2S exhibits a higher performance than those pretreated with H2 or He. Although the feed concentrations of C2H4:SO2 being 3000:3000 ppm provide a higher conversion of SO2, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C2H4 temperature-programmed desorption (C2H4-TPD) and SO2-TPD desorption patterns illustrate that Fe2O3/CeO2 can adsorb and desorb C2H4 and SO2 more easily than can Fe2O3/γ-Al2O3. Moreover, the SO2-TPD patterns further show that Fe2O3/γ-Al2O3 is more seriously inhibited by SO2. These findings may properly explain why Fe2O3/CeO2 has a higher activity for the reduction of SO2.  相似文献   

7.
The reduction of nitrogen monoxide by propene on V2O5/ZrO2 doped with or without calcium has been studied by FTIR spectroscopy as well as by analysis of the reaction products. Considerable promoting effect of calcium doping on the reduction of nitrogen monoxide by propene was observed on the V2O5/ZrO2 catalysts. For the reaction of a mixture of NO+C3H6, carbonyl and carboxylate species were observed above 373 K, although nitrate species formed at room temperature on V2O5/ZrO2 doped with calcium. No bands due to a compound including both carbon and nitrogen atoms were observed. Thus, the redox mechanism, i.e. propene reduces the catalyst and nitrogen monoxide oxidizes the catalyst, is confirmed on V2O5/ZrO2 catalysts doped with or without calcium. The analysis of the V=O band in the region of 1100–900 cm−1 indicates that this promotion is mainly due to new V=O species formed by the addition of calcium onto the catalyst. This species is easily reproduced in comparison with the other V=O species on the surface in the reoxidation process of the catalyst.  相似文献   

8.
The kinetics of oxidation of a light hydrocarbon (C2H4) were studied on catalysts comprising of combinations of one of three metals, Pt, Pd or Rh supported on five different supports, that is, SiO2, γ-Al2O3, ZrO2 (8% Y2O3), TiO2 or TiO2 (W6+). Significant variation of turnover frequency with the carrier was observed, which cannot be explained by structure sensitivity considerations and is attributed to interactions between the metal crystallites and the carrier. The catalytic activity of these metal-support combinations was investigated over a wide range of partial pressures of ethylene and oxygen. In a separate set of experiments, the kinetics of C2H4 oxidation were also investigated on polycrystalline Rh films interfaced with ZrO2 (8 mol% Y2O3) solid electrolyte in a galvanic cell of the type: C2H4, O2, Rh/YSZ/Pt, air, during regular open-circuit conditions as well as under Non-Faradic Electrochemical Modification of Catalytic Activity (NEMCA), that is, closed-circuit conditions. Up to 100-fold increase in catalytic activity was observed by supplying O2− ions to the catalyst surface via positive potential application to the catalyst. The observed kinetic behavior upon increasing catalyst potential parallels qualitatively the observed alteration of turnover frequency with variation of the support of the Rh crystallites.  相似文献   

9.
The hydrogenation of CO over an Rh vanadate (RhVO4) catalyst supported on SiO2 (RhVO4/SiO2) has been investigated after H2 reduction at 500°C, and the results are compared with those of vanadia-promoted (V2O5–Rh/SiO2) and unpromoted Rh/SiO2 catalysts. The mean size of Rh particles, which were dispersed by the decomposition of RhVO4 after the H2 reduction, was smaller (41 Å) than those (91–101 Å) of V2O5–Rh/SiO2 and Rh/SiO2 catalysts. The RhVO4/SiO2 catalyst showed higher activity and selectivity to C2 oxygenates than the unpromoted Rh/SiO2 catalyst after the H2 pretreatment. The CO conversion of the RhVO4/SiO2 catalyst was much higher than that of V2O5–Rh/SiO2 catalyst, and the yield of C2 oxygenates increased. We also found that the RhVO4/SiO2 catalyst can be regenerated by calcination or O2 treatment at high temperature after the reaction.  相似文献   

10.
The selective catalytic reduction (SCR) of NOx assisted by propene is investigated on Pd/Ce0.68Zr0.32O2 catalysts (Pd/CZ), and is compared, under identical experimental conditions, with that found on a Pd/SiO2 reference catalyst. Physico-chemical characterisation of the studied catalysts along with their catalytic properties indicate that Pd is not fully reduced to metallic Pd for the Pd/CZ catalysts. This study shows that the incorporation of Pd to CZ greatly promotes the reduction of NO in the presence of C3H6. These catalysts display very stable deNOx activity even in the presence of 1.7% water, the addition of which induces a reversible deactivation of about 10%. The much higher N2 selectivity obtained on Pd/CZ suggests that the lean deNOx mechanism occurring on these catalysts is different from that occurring on Pd0/SiO2. A detailed mechanism is proposed for which CZ achieves both NO oxidation to NO2 and NO decomposition to N2, whereas PdOx activates C3H6 via ad-NO2 species, intermediately producing R-NOx compounds that further decompose to NO and CxHyOz. The role of the latter oxygenates is to reduce CZ to provide the catalytic sites responsible for NO decomposition. The proposed C3H6-assisted NO decomposition mechanism stresses the key role of NO2, R-NOx and CxHyOz as intermediates of the SCR of NOx by hydrocarbons.  相似文献   

11.
The activity and selectivity of rhenium promoted cobalt Fischer–Tropsch catalysts supported on Al2O3, TiO2 and SiO2 have been studied in a fixed-bed reactor at 483 K and 20 bar. Exposure of the catalysts to water added to the feed deactivates the Al2O3 supported catalyst, while the activity of the TiO2 and SiO2 supported catalysts increased. However, at high concentrations of water both the SiO2 and TiO2 supported catalyst deactivated. Common for all catalysts was an increase in C5+ selectivity and a decrease in the CH4 selectivity by increasing the water partial pressure. The catalysts have been characterized by scanning transmission electron microscope (STEM), BET, H2 chemisorption and X-ray diffraction (XRD).  相似文献   

12.
Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。  相似文献   

13.
Mn effect and characterization on γ-Al2O3-, -Al2O3- and SiO2-supported Ru catalysts were investigated for Fischer–Tropsch synthesis under pressurized conditions. In the slurry phase Fischer–Tropsch reaction, γ-Al2O3 catalysts showed higher performance on CO conversion and C5+ selectivity than -Al2O3 and SiO2 catalysts. Moreover, Ru/Mn/γ-Al2O3 exhibited high resistance to catalyst deactivation and other catalysts were deactivated during the reaction. From characterization results on XRD, TPR, TEM, XPS and pore distribution, Ru particles were clearly observed over the catalysts, and γ-Al2O3 catalysts showed a moderate pore and particle size such as 8 nm, where -Al2O3 and SiO2 showed highly dispersed ruthenium particles. The addition of Mn to γ-Al2O3 enhanced the removal of chloride from RuCl3, which can lead to the formation of metallic Ru with moderate particle size, which would be an active site for Fischer–Tropsch reaction. Concomitantly, manganese chloride is formed. These schemes can be assigned to the stable nature of Ru/Mn/γ-Al2O3 catalyst.  相似文献   

14.
Selective catalytic reduction of NOx by C3H6 in the presence of H2 over Ag/Al2O3 was investigated using in situ DRIFTS and GC–MS measurements. The addition of H2 promoted the partial oxidation of C3H6 to enolic species, the formation of –NCO and the reactions of enolic species and –NCO with NOx on Ag/Al2O3 surface at low temperatures. Based on the results, we proposed reaction mechanism to explain the promotional effect of H2 on the SCR of NOx by C3H6 over Ag/Al2O3 catalyst.  相似文献   

15.
The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C2 hydrocarbons and by-products were CO and H2. Methane conversion and the yield of C2 hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C2 hydrocarbons decreased. The synergism of La2O3/γ-Al2O3 and plasma gave methane conversion of 24.9% and C2 hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C2 hydrocarbons changed by using Pd-La2O3/γ-Al2O3 catalyst, the major C2 product was ethylene.  相似文献   

16.
Molybdenum impregnated HZSM-5 zeolite catalysts with MoO3 loading from 1 to 8 wt.% were studied in detail for the selective catalytic reduction (C2H2-SCR) of NO by acetylene. A 83.9% of NO could be removed by the reductant at 350 °C under 1600 ppm of NO, 800 ppm of C2H2 and 9.95% of O2 in He over 2%MoO3/HZSM-5 catalyst with a specific activity of in NO elimination and the competitiveness factor (c.f.) of 33.6% for the reductant. The NO elimination level and the c.f. value were ca. 3–4 times as high as those using methane or propene as reductant over the catalyst in the same reaction condition. About same reaction rate was estimated in NO oxidation as that in the NO reduction over each xMoO3/HZSM-5 (x = 0–8%) catalyst, which confirms that NO2 is a crucial intermediate for the aimed reaction over the catalysts. Appropriate amount of Mo incorporation to HZSM-5 considerably enhanced the title reaction, both by accelerating the intermediate formation and by strengthening the adsorption NOx on the catalyst surface under the reaction conditions. Rather lower adsorption tendency of acetylene compared with propene on the catalysts explains the catalyst's steady performance in the C2H2-SCR of NO and rapid deactivation in the C3H6-SCR of NO.  相似文献   

17.
Experimental proofs of a free radical mechanism in methane oxidative coupling, with homolytic rupture of the C---H bond are given. High concentrations of free radical sites are produced by mechanical milling of SiO2. A study of C1---C3alkanes interaction with these sites allows to simulate the, processes of alkanes oxidation and oxidative dehydrogenation. The reactivity of ethane and propane is higher than that of methane in accordance with the Polanyi-Semenov rule. Oxidative dehydrogenation of ethane is studied on Cd-containing zeolites. CH4, C2H6 and C3H8 oxidative dehydrogenation by O2 or CO2 is studied on a MNO/SiO2 catalyst. The initiation of radical reactions of hydrocarbons on Cl-containing catalysts proceeds via chlorine atoms generation.  相似文献   

18.
Surface-phase ZrO2 on SiO2 (SZrOs) and surface-phase La2O3 on Al2O3 (SLaOs) were prepared with various loadings of ZrO2 and La2O3, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH4/CO2 reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al2O3 and Pt/SiO2 catalysts. CO2 or CH4 pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO2 to form a stable surface-phase oxide. The lanthana cannot be spread well on Al2O3, but it forms a stable amorphous oxide with Al2O3. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO2 and Pt/Al2O3 by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO2 and Pt/Al2O3 catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO2 adsorbed on the basic sites of SZrOs and SLaOs.  相似文献   


19.
The effectiveness of Ag/Al2O3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al2O3, and Al(OH)3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O2, NO + O2-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C3H6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C3H6 conversion was achieved over Ag/Al2O3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al2O3 (I) is deemed to be crucial for NO selective reduction into N2. By contrast, a high C3H6 conversion simultaneously with a moderate N2 yield was observed over Ag/Al2O3 (II) prepared from a γ-Al2O3 source. The larger particles of AgmO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al2O3 (III) was obtained via employing a Al(OH)3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al2O3 (I). A subsequent calcination of Ag/Al2O3 (III) at 800 °C led to the generation of Ag/Al2O3 (IV) catalyst yielding a significant enhancement in both N2 yield and C3H6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al2O3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al2O3 (II and V) > Ag/Al2O3 (IV) > Ag/Al2O3 (I) > Ag/Al2O3 (III) and Al2O3 (I). The formation of nitrate species is an important step for the deNOx process, which can be promoted by increasing O2 feed concentration as evidenced by NO + O2-TPD study for Ag/Al2O3 (I), achieving a better catalytic performance.  相似文献   

20.
Plasma/catalyst combination is an active solution to reach high conversion rates at low energetic cost. TiO2 is one of the catalysts frequently used in dielectric barrier discharges. Plasma/TiO2 synergy was already exhibited but the mechanisms still have to be understood. This work distinguishes three main effects involved in the synergy: (a) effect of catalyst on the injected power, (b) the effect of porosity on C2H2 oxidation, and (c) the photocatalytic degradation of C2H2 on TiO2 under plasma exposure. Different glass fibres-based catalytic materials coated with SiO2 and/or TiO2 nano-particles are used to separate these three contributions regarding to C2H2 conversion. It is reported that at constant voltage the injected power is mainly increased by the presence of glass fibres. C2H2 oxidation is mainly enhanced by the macroporosity of glass fibres and in a minor way by the nano-particles. The production of O atoms close to the surface is probably responsible for the higher C2H2 removal efficiency with porous material. The photocatalytic activity of TiO2 is negligible in the plasma except if additional UV lamps are used to activate TiO2. With external UV, photocatalytic activity is more efficient in the plasma phase than in a neutral gas phase. This plasma/photocatalysis synergy is due to the use of O atoms in photocatalytic mechanisms.  相似文献   

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