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1.
Effect of additives, In2O3, SnO2, CoO, CuO and Ag, on the catalytic performance of Ga2O3–Al2O3 prepared by sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. As for the reaction in the absence of H2O, CoO, CuO and Ag showed good additive effect. When H2O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga2O3–Al2O3 was depressed considerably, while an intensifying effect of H2O was observed for In2O3- and SnO2-doped Ga2O3–Al2O3. Of several metal oxide additives, In2O3-doped Ga2O3–Al2O3 showed the highest activity for NO reduction by propene in the presence of H2O. Kinetic studies on NO reduction over In2O3–Ga2O3–Al2O3 revealed that the rate-determining step in the absence of H2O is the reaction of NO2 formed on Ga2O3–Al2O3 with C3H6-derived species, whereas that in the presence of H2O is the formation of C3H6-derived species. We presumed the reason for the promotional effect of H2O as follows: the rate for the formation of C3H6-derived species in the presence of H2O is sufficiently fast compared with that for the reaction of NO2 with C3H6-derived species in the absence of H2O. Although the retarding effect of SO2 on the activity was observed for all of the catalysts, SnO2–Ga2O3–Al2O3 showed still relatively high activity in the lower temperature region.  相似文献   

2.
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   

3.
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   

4.
Catalytic performance of Sn/Al2O3 catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NOx by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO2 had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al2O3 (SG) catalyst, and the maximum NO2 conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NOx desorption accompanied with O2 around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H2O and SO2 at low temperature, and the temperature window was also broadened in the presence of H2O and SO2, however the NOx desorption and NO conversion decreased sharply on the 300 ppm SO2 treated catalyst, the catalytic activity was inhibited by the presence of SO2 due to formation of sulfate species (SO42−) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al2O3 (SG) was not decreased in the presence of large oxygen.  相似文献   

5.
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   

6.
Ag-based catalysts supported on various metal oxides, Al2O3, TiO2, and TiO2–Al2O3, were prepared by the sol–gel method. The effect of SO2 on catalytic activity was investigated for NO reduction with propene under lean burn condition. The results showed the catalytic activities were greatly enhanced on Ag/TiO2–Al2O3 in comparison to Ag/Al2O3 and Ag/TiO2, especially in the low temperature region. Application of different characterization techniques revealed that the activity enhancement was correlated with the properties of the support material. Silver was highly dispersed over the amorphous system of TiO2–Al2O3. NO3 rather than NO2 or NOx reacted with the carboxylate species to form CN or NCO. NO2 was the predominant desorption species in the temperature programmed desorption (TPD) of NO on Ag/TiO2–Al2O3. More amount of formate (HCOO) and CN were generated on the Ag/TiO2–Al2O3 catalyst than the Ag/Al2O3 catalyst, due to an increased number of Lewis acid sites. Sulfate species, resulted from SO2 oxidation, played dual roles on catalytic activity. On aged samples, the slow decomposition of accumulated sulfate species on catalyst surface led to poor NO conversion due to the blockage of these species on active sites. On the other hand, catalytic activity was greatly enhanced in the low temperature region because of the enhanced intensity of Lewis acid site caused by the adsorbed sulfate species. The rate of sulfate accumulation on the Ag/TiO2–Al2O3 system was relatively slow. As a consequence, the system showed superior capability for selective adsorption of NO and SO2 toleration to the Ag/Al2O3 catalyst.  相似文献   

7.
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   

8.
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   

9.
Combined effect of H2O and SO2 on V2O5/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH3 at lower temperatures was studied. In the absence of SO2, H2O inhibits the catalytic activity, which may be attributed to competitive adsorption of H2O and reactants (NO and/or NH3). Although SO2 promotes the SCR activity of the V2O5/AC catalyst in the absence of H2O, it speeds the deactivation of the catalyst in the presence of H2O. The dual effect of SO2 is attributed to the SO42− formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H2O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H2O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V2O5 loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h−1 and temperature of 250 °C.  相似文献   

10.
The adsorption of HCN on, its catalytic oxidation with 6% O2 over 0.5% Pt/Al2O3, and the subsequent oxidation of strongly bound chemisorbed species upon heating were investigated. The observed N-containing products were N2O, NO and NO2, and some residual adsorbed N-containing species were oxidized to NO and NO2 during subsequent temperature programmed oxidation. Because N-atom balance could not be obtained after accounting for the quantities of each of these product species, we propose that N2 and was formed. Both the HCN conversion and the selectivity towards different N-containing products depend strongly on the reaction temperature and the composition of the reactant gas mixture. In particular, total HCN conversion reaches 95% above 250 °C. Furthermore, the temperature of maximum HCN conversion to N2O is located between 200 and 250 °C, while raising the reaction temperature increases the proportion of NOx in the products. The co-feeding of H2O and C3H6 had little, if any effect on the total HCN conversion, but C3H6 addition did increase the conversion to NO and decrease the conversion to NO2, perhaps due to the competing presence of adsorbed fragments of reductive C3H6. Evidence is also presented that introduction of NO and NO2 into the reactant gas mixture resulted in additional reaction pathways between these NOx species and HCN that provide for lean-NOx reduction coincident with HCN oxidation.  相似文献   

11.
A novel activated carbon-supported vanadium oxide catalyst was studied for SCR of NO with NH3 at low temperatures (100 – 250°C). The effects of reaction temperature, preparation conditions and SO2 on SCR activity were evaluated. The results show that this catalyst has a high catalytic activity for NO–NH3–O2 reaction at low temperatures. Preoxidation of the calcined catalyst helps improve catalytic activity. V2O5 loading, other than calcination temperature, gives a significant influence on the activity. SO2 in the flue gas does not de-activate the catalyst but improves it. A stability test of more than 260 h shows that the catalyst is highly active and stable in the presence of SO2.  相似文献   

12.
Reaction activities of several developed catalysts for NO oxidation and NOx (NO + NO2) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co3O4 based catalysts are the most active ones for both NO oxidation and NOx reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co3O4 catalyst, the effects of calcination temperatures, SO2 concentration, optimum SV for 50% conversion of NO to NO2 were determined. Also, Co3O4 based catalysts (Co3O4-WO3) exhibit significantly higher conversion than all the developed DeNOx catalysts (supported/unsupported) having maximum conversion of NOx even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N2O formation over Co3O4-WO3 catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N2O over all the catalysts. The effect of SO2 concentration on NOx reduction is found to be almost negligible may be due to the presence of WO3 that resists SO2 oxidation.  相似文献   

13.
The effect of oxygen concentration on the pulse and steady-state selective catalytic reduction (SCR) of NO with C3H6 over CuO/γ-Al2O3 has been studied by infrared spectroscopy (IR) coupled with mass spectroscopy studies. IR studies revealed that the pulse SCR occurred via (i) the oxidation of Cu0/Cu+ to Cu2+ by NO and O2, (ii) the co-adsorption of NO/NO2/O2 to produce Cu2+(NO3)2, and (iii) the reaction of Cu2+(NO3)2 with C3H6 to produce N2, CO2, and H2O. Increasing the O2/NO ratio from 25.0 to 83.4 promotes the formation of NO2 from gas phase oxidation of NO, resulting in a reactant mixture of NO/NO2/O2. This reactant mixture allows the formation of Cu2+(NO3)2 and its reaction with the C3H6 to occur at a higher rate with a higher selectivity toward N2 than the low O2/NO flow. Both the high and low O2/NO steady-state SCR reactions follow the same pathway, proceeding via adsorbed C3H7---NO2, C3H7---ONO, CH3COO, Cu0---CN, and Cu+---NCO intermediates toward N2, CO2, and H2O products. High O2 concentration in the high O2/NO SCR accelerates both the formation and destruction of adsorbates, resulting in their intensities similar to the low O2/NO SCR at 523–698 K. High O2 concentration in the reactant mixture resulted in a higher rate of destruction of the intermediates than low O2 concentration at temperatures above 723 K.  相似文献   

14.
The catalytic behavior of the V-M/AC (M=W, Mo, Zr, and Sn) catalysts were studied for the NO reduction with ammonia at low temperatures, especially in the presence of SO2. The presence of the metal oxides does not increase the V2O5/AC activity but decreases it. Except V-Mo/AC, the other catalysts are promoted by SO2 at 250°C, especially for V-Sn/AC. However, the promoting effect of SO2 is gradually depressed by catalyst deactivation. Changes in catalyst preparation method can improve the catalyst stability in short-term but cannot completely prevent the catalyst from a long-term deactivation. Mechanisms of the promoting effect and the deactivation of V-Sn/AC catalyst by SO2 were studied using Fourier transform infrared spectroscopy (FT-IR) spectra and measurement of catalyst surface area and pore volume. The results showed that both the SO2 promotion and deactivation are associated with the formation of sulfate species on the catalyst surface. In the initial period of the selective catalytic reduction (SCR) reaction in the presence of SO2, the formed sulfate species provide new acid sites to enhance ammonia adsorption and thus the catalytic activity. However, as the SCR reaction proceeds, excess amount of sulfate species and then ammonium-sulfate salts are formed which is stabilized by the presence of tin oxide, resulting in gradual plugging of the pore structures and the catalyst deactivation.  相似文献   

15.
The effect of the addition of a second fuel such as CO, C3H8 or H2 on the catalytic combustion of methane was investigated over ceramic monoliths coated with LaMnO3/La-γAl2O3 catalyst. Results of autothermal ignition of different binary fuel mixtures characterised by the same overall heating value show that the presence of a more reactive compound reduces the minimum pre-heating temperature necessary to burn methane. The effect is more pronounced for the addition of CO and very similar for C3H8 and H2. Order of reactivity of the different fuels established in isothermal activity measurements was: CO>H2≥C3H8>CH4. Under autothermal conditions, nearly complete methane conversion is obtained with catalyst temperatures around 800 °C mainly through heterogeneous reactions, with about 60–70 ppm of unburned CH4 when pure methane or CO/CH4 mixtures are used. For H2/CH4 and C3H8/CH4 mixtures, emissions of unburned methane are lower, probably due to the proceeding of CH4 homogeneous oxidation promoted by H and OH radicals generated by propane and hydrogen pyrolysis at such relatively high temperatures.

Finally, a steady state multiplicity is found by decreasing the pre-heating temperature from the ignited state. This occurrence can be successfully employed to pilot the catalytic ignition of methane at temperatures close to compressor discharge or easily achieved in regenerative burners.  相似文献   


16.
G. Centi  F. Vazzana 《Catalysis Today》1999,53(4):6695-693
The catalytic behavior in N2O reduction by propane in the presence of O2, H2O and SO2 of Fe/ZSM-5 catalysts prepared by ion exchange and chemical vapour deposition (CVD) is reported. The catalyst prepared by CVD shows a lower dependence of the rate of selective N2O reduction on the decrease in C3H8 to N2O ratio in the feed and a higher resistance to deactivation by SO2 in accelerated durability tests with high SO2 concentration (500 ppm). This catalyst shows stable catalytic behavior in the presence of SO2 for more than 600 h of time-on-stream. Characterization of the catalysts by UV–VIS–NIR diffuse reflectance indicates that the poor performances of the sample prepared by ion exchange could be related to the presence of highly clustered Fe3+ species, in this catalyst. On the other hand, Fe2O3 particles are not present in the sample prepared by CVD while mainly isolated Fe3+ ions and iron-oxide nanoclusters are present.  相似文献   

17.
A La–Sr–Cu–O–S system with K2NiF4 perovskite-type structure has been studied as a novel SOx-resistant combustion catalyst. The XRD result implied that sulfur is incorporated into the structure as non-sulfate-type cations. An introduction of sulfur with highly positive valence (S6+ or S4+) into the lattice requires the charge compensation by decreasing the oxidation number of Cu. This is accompanied by the creation of more reducible Cu species, which would achieve the light-off of catalytic C3H6 oxidation at lower temperatures. More important feature of sulfur-containing compounds is that the catalytic C3H6 oxidation was significantly accelerated by addition of SO2 to the gas feed. The catalytic performance for the oxidation of C3H6 and CO and the reduction of NO was finally evaluated in a simulated automotive exhaust in the presence of SO2.  相似文献   

18.
A series of La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O2, NO + O2, C3H6, in the absence or presence of 5% H2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C3H6, 1% O2, 0 or 10% H2O, and 50,000 h−1 space velocity. The objective was to investigate the influence of H2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N2 yield, and 90% C3H6 conversion) was achieved at 600 °C over LaFe0.8Cu0.2O3 under a dry feed stream. With the exposure of LaFe0.8Cu0.2O3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N2 yield, and 86% C3H6 conversion. A competitive adsorption between H2O vapor with O2 and NO molecules at anion vacancies over LaFe0.8Cu0.2O3 was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C3H6 + NO + O2 reaction. This H2O deactivation was also verified to be strictly reversible by removing steam from the feed.  相似文献   

19.
Nanoparticles of CexZr1−xO2 (x = 0.75, 0.62) were prepared by the oxidation-coprecipitation method using H2O2 as an oxidant, and characterized by N2 adsorption, XRD and H2-TPR. CexZr1−xO2 prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of CexZr1−xO2 increased, but thermal stability of CexZr1−xO2 decreased. The surface area of Ce0.62Zr0.38O2 was 41.2 m2/g after calcination in air at 900 °C for 6 h. TPR results showed the formation of solid solution promoted the reduction of CeO2, and the reduction properties of CexZr1−xO2 were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce0.75Zr0.25O2 was used as the active washcoat and Pd loading was 0.7 g/L. In the test of Air/Fuel, the conversion of C3H8 was close to 100% and NO was completely converted at λ < 1.025. The high conversion of C3H8 was induced by the steam reform and dissociation adsorption reaction of C3H8. Pd-only catalyst using Ce0.75Zr0.25O2 as active washcoat showed high light off activity, the reaction temperatures (T50) of 50% conversion of CO, C3H8 and NO were 180, 200 and 205 °C, respectively. However, the conversions of C3H8 and NO showed oscillation with continuously increasing the reaction temperature. The presence of La2O3 in washcoat decreased the light off activity and suppressed the oscillation of C3H8 and NO conversion. After being aged at 900 °C for 4 h, the operation windows of catalysts shifted slightly to rich burn. The presence of La2O3 in active washcoat can enhance the thermal stability of catalyst significantly.  相似文献   

20.
The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al2O3 with a bulk oxide has been investigated. The oxides studied were: Co3O4, Mn2O3, Cr2O3, CuO, Fe2O3, NiO, CeO2, SnO2, ZnO and V2O5. Under lean C3H6-SCR conditions, these oxides (with the exception of SnO2) convert selectively NO to NO2. When mechanically mixed with Au/Al2O3, the Mn2O3 and Co3O4 oxides and, to a much greater extent, CeO2 act synergistically with this catalyst greatly enhancing its SCR performance. It was found that their synergistic action is not straightforwardly related to their activity for NO oxidation to NO2. The exhibited catalytic synergy may be due to the operation of either remote control or a bifunctional mechanism. In the later case, the key intermediate must be a short-lived compound and not the NO2 molecule in gas-phase.  相似文献   

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