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1.
A mean field model, for storage and desorption of NO x in a Pt/BaO/Al 2O 3 catalyst is developed using data from flow reactor experiments. This relatively complex system is divided into five smaller sub-systems and the model is divided into the following steps: (i) NO oxidation on Pt/Al 2O 3; (ii) NO oxidation on Pt/BaO/Al 2O 3; (iii) NO x storage on BaO/Al 2O 3; (iv) NO x storage on Pt/BaO/Al 2O 3 with thermal regeneration and (v) NO x storage on Pt/BaO/Al 2O 3 with regeneration using C 3H 6. In this paper, we focus on the last sub-system. The kinetic model for NO x storage on Pt/BaO/Al 2O 3 was constructed with kinetic parameters obtained from the NO oxidation model together with a NO x storage model on BaO/Al 2O 3. This model was not sufficient to describe the NO x storage experiments for the Pt/BaO/Al 2O 3, because the NO x desorption in TPD experiments was larger for Pt/BaO/Al 2O 3, compared to BaO/Al 2O 3. The model was therefore modified by adding a reversible spill-over step. Further, the model was validated with additional experiments, which showed that NO significantly promoted desorption of NO x from Pt/BaO/Al 2O 3. To this NO x storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO 2 and C 3H 6. The main reactions for continuous reduction of NO x occurs on Pt by reactions between hydrocarbon species and NO in the model. The model is also able to describe the reduction phase, the storage and NO breakthrough peaks, observed in experiments. 相似文献
2.
Selective catalytic reduction of NO x by C 3H 6 in the presence of H 2 over Ag/Al 2O 3 was investigated using in situ DRIFTS and GC–MS measurements. The addition of H 2 promoted the partial oxidation of C 3H 6 to enolic species, the formation of –NCO and the reactions of enolic species and –NCO with NO x on Ag/Al 2O 3 surface at low temperatures. Based on the results, we proposed reaction mechanism to explain the promotional effect of H 2 on the SCR of NO x by C 3H 6 over Ag/Al 2O 3 catalyst. 相似文献
3.
The reduction of NO x by hydrogen under lean burn conditions over Pt/Al 2O 3 is strongly poisoned by carbon monoxide. This is due to the strong adsorption and subsequent high coverage of CO, which significantly increases the temperature required to initiate the reaction. Even relatively small concentrations of CO dramatically reduce the maximum NO x conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al 2O 3. In this case, although pure H 2 and pure CO are ineffective for NO x reduction under lean burn conditions, H 2/CO mixtures are very effective. With a realistic (1:3) H 2:CO ratio, typical of actual exhaust gas, Pd/Al 2O 3 is significantly more active than Pt/Al 2O 3, delivering 45% NO x conversion at 160 °C, compared to >15% for Pt/Al 2O 3 under identical conditions. The nature of the support is also critically important, with Pd/Al 2O 3 being much more active than Pd/SiO 2. Possible mechanisms for the improved performance of Pd/Al 2O 3 in the presence of H 2+CO are discussed. 相似文献
4.
This paper deals with the activity of bimetallic potassium–copper and potassium–cobalt catalysts supported on alumina for the reduction of NO x with soot from simulated diesel engine exhaust. The effect of the reaction temperature, the soot/catalyst mass ratio and the presence of C 3H 6 has been studied. In addition, the behavior of two monometallic catalysts supported on zeolite beta (Co/beta and Cu/beta), previously used for NO x reduction with C 3H 6, as well as a highly active HC-SCR catalyst (Pt/beta) has been tested for comparison. The preliminary results obtained in the absence of C 3H 6 indicate that, at temperatures between 250 and 400 °C, the use of bimetallic potassium catalysts notably increases the rate of NO x reduction with soot evolving N 2 and CO 2 as main reaction products. At higher temperatures, the catalysts mainly favor the direct soot combustion with oxygen. In the presence of C 3H 6, an increase in the activity for NO x reduction has been observed for the catalyst with the highest metal content. At 450 °C, the copper-based catalysts (Cu/beta and KCu2/Al 2O 3) show the highest activity for both NO x reduction (to N 2 and CO 2) and soot consumption. The Pt/beta catalyst does not combine, at any temperature, a high NO x reduction with a high soot consumption rate. 相似文献
5.
The influence of SO 2, H 2S and COS in low concentrations on the deactivation of Pt/Rh/BaO/Al 2O 3 NO x storage catalysts was investigated. Different samples of the catalyst were exposed to synthetic gas mixtures mimicking lean/rich engine cycling in a mixed lean application at 400 °C. The lean gas mixture contained 8 vol.% O 2, 500 vol-ppm C 3H 6 and 400 vol-ppm NO balanced to 100 vol.% with Ar. The rich excursions were performed by switching off the oxygen supply. Sulphur, 25 vol-ppm of either SO 2, H 2S or COS, was added to the gas flow either during the lean, the rich or both periods. This procedure aimed at investigating the influence of the exposure conditions and therefore the lean and rich periods were kept equally long (5 min). In addition, thermodynamical calculations for the prevailing conditions were performed. It was concluded that all sulphur compounds investigated, i.e. SO2, H2S and COS, had similar, negative impact on the NOx storage ability of the catalyst and that they all showed increased deactivation rates during rich exposure compared to lean. During lean exposure, all sulphur carriers showed similar behaviour, while H2S and COS caused severe loss of noble metal activity during rich exposure. 相似文献
6.
The reduction of NO under cyclic “lean”/“rich” conditions was examined over two model 1 wt.% Pt/20 wt.% BaO/Al 2O 3 and 1 wt.% Pd/20 wt.% BaO/Al 2O 3 NO x storage reduction (NSR) catalysts. At temperatures between 250 and 350 °C, the Pd/BaO/Al 2O 3 catalyst exhibits higher overall NO x reduction activity. Limited amounts of N 2O were formed over both catalysts. Identical cyclic studies conducted with non-BaO-containing 1 wt.% Pt/Al 2O 3 and Pd/Al 2O 3 catalysts demonstrate that under these conditions Pd exhibits a higher activity for the oxidation of both propylene and NO. Furthermore, in situ FTIR studies conducted under identical conditions suggest the formation of higher amounts of surface nitrite species on Pd/BaO/Al 2O 3. The IR results indicate that this species is substantially more active towards reaction with propylene. Moreover, its formation and reduction appear to represent the main pathway for the storage and reduction of NO under the conditions examined. Consequently, the higher activity of Pd can be attributed to its higher oxidation activity, leading both to a higher storage capacity ( i.e., higher concentration of surface nitrites under “lean” conditions) and a higher reduction activity ( i.e., higher concentration of partially oxidized active propylene species under “rich” conditions). The performance of Pt and Pd is nearly identical at temperatures above 375 °C. 相似文献
7.
The catalytic performance and the behavior of NO x storage and reduction (NSR) over a model catalyst for lean-burn gasoline engines have been mainly investigated and be discussed based on the temperature and reducing agents use in this study. The experimental results have shown that the NO x storage amount in the lean atmosphere was the same as the NO x reduction amount from the subsequent rich spike (RS) above the temperature of 400 °C, while the former was greater than the latter below the temperature of 400 °C. This indicated that when the temperature was below 400 °C compared with the NO x storage stage, the reduction of the stored NO x is somehow restricted. We found that the reduction efficiencies with the reducing agents decrease in the order H 2 > CO > C 3H 6 below 400 °C, thus not all of the NO x storage sites could be fully regenerated even using an excessive reducing agent of CO or C 3H 6, which was supplied to the NSR catalyst, while all the NO x storage sites could be fully regenerated if an adequate amount of H 2 was supplied. We also verified that the H 2 generation more favorably occurred through the water gas shift reaction than through the steam reforming reaction. This difference in the H 2 generation could reasonably explain why CO was more efficient for the reduction of the stored NO x than C 3H 6, and hinted as a promising approach to enhance the low-temperature performance of the current NSR catalysts though promoting the H 2 generation reaction. 相似文献
8.
Pt-based catalysts have been prepared using supports of different nature (γ-Al 2O 3, ZSM-5, USY, and activated carbon (ROXN)) for the C 3H 6-SCR of NO x in the presence of excess oxygen. Nitrogen adsorption at 77 K, pH measurements, temperature-programmed desorption of propene, and H 2 chemisorption were used for the characterization of the different supports and catalysts. The performance of these catalysts has been compared in terms of de-NO x activity, hydrocarbon adsorption and combustion at low temperature, and selectivity to N 2. Maximum NO x conversions for all the catalysts were achieved in the temperature range of 200–250°C. The order of activity was, Pt-USY>Pt/ROXNPt-ZSM-5Pt/Al 2O 3. At temperatures above 300°C only Pt/ROXN maintains a high activity caused by the consumption of the support, while the other catalysts present a strong deactivation. Propene combustion starts at the same temperature for all the catalytic systems (160°C). Complete hydrocarbon combustion is directly related to the acidity of the support, thus determining the temperature of the maximum NO x reduction. The support play an important role in the reaction mechanism through the hydrocarbon activation. N 2O formation was observed for all the catalysts. N 2 selectivity ranges from 15 to 30% with the order, Pt/ROXN>Pt-USYPt/Al 2O 3>Pt-ZSM-5. The catalytic systems exhibit a stable operation under isothermal conditions during time-on-stream experiments. 相似文献
9.
The adsorption of HCN on, its catalytic oxidation with 6% O 2 over 0.5% Pt/Al 2O 3, and the subsequent oxidation of strongly bound chemisorbed species upon heating were investigated. The observed N-containing products were N 2O, NO and NO 2, and some residual adsorbed N-containing species were oxidized to NO and NO 2 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 N 2 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 N 2O is located between 200 and 250 °C, while raising the reaction temperature increases the proportion of NO x in the products. The co-feeding of H 2O and C 3H 6 had little, if any effect on the total HCN conversion, but C 3H 6 addition did increase the conversion to NO and decrease the conversion to NO 2, perhaps due to the competing presence of adsorbed fragments of reductive C 3H 6. Evidence is also presented that introduction of NO and NO 2 into the reactant gas mixture resulted in additional reaction pathways between these NO x species and HCN that provide for lean-NO x reduction coincident with HCN oxidation. 相似文献
10.
For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant ( 15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NO x storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al 2O 3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H 2 and/or CO and NO on reduced Rh and/or Pt sites. The second N 2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NO x, gas phase NO x or O 2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H 2. The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant. 相似文献
11.
Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH 4 and C 3H 8, in order to investigate the effect of the concentration of the fuels, O 2 and H 2O on NO x emission and combustion characteristics. Among the hexaaluminate catalysts, Sr 0.8La 0.2MnAl 11O 19− prepared by the alkoxide method exhibited the highest activity for methane combustion and low NO x emission capability. NO x emission at 1500 °C was increased linearly with O 2 concentration, whereas water vapor addition decreased NO x emission in CH 4 combustion over the Sr 0.8La 0.2MnAl 11O 19− catalyst. In the catalytic combustion of C 3H 8 over the Sr 0.8La 0.2MnAl 11O 19− catalyst, the amount of NO x emitted was raised in the temperature range between 1000 and 1500 °C when the C 3H 8 concentration increased from 1 to 2 vol.%. It was found that NO x emission in this temperature range was reduced effectively by adding water vapor. 相似文献
12.
The NO x storage and reduction functions of a Pt–Ba/Al 2O 3 “NO x storage–reduction” catalyst has been investigated in the present work by applying the transient response and the temperature programmed reaction methods, by using propylene as the reducing agent. It is found that: (i) the storage of NO x occurs first at BaO and then at BaCO 3, which are the most abundant sites following regeneration of catalyst with propylene; (ii) the overall storage process at BaCO 3 is slower than at BaO; (iii) CO 2 inhibits the NO x storage at low temperatures; (iv) the amount of NO x stored up to catalyst saturation at 350 °C corresponds to 17.6% of Ba; (v) the reduction of stored NO x groups is fast and is limited by the concentration of propylene in the investigated T range (250–400 °C); (vi) selectivity to N 2 is almost complete at 400 °C but is significantly lower at 300 °C due to the formation of NO which can be tentatively ascribed to the presence of unselective Pt–O species. 相似文献
13.
A multi-component NO x-trap catalyst consisting of Pt and K supported on γ-Al 2O 3 was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H 2O and CO 2 on NO x storage. The Al 2O 3 support was shown to have NO x trapping capability with and without Pt present (at 250 °C Pt/Al 2O 3 adsorbs 2.3 μmols NO x/m 2). NO x is primarily trapped on Al 2O 3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO x/m 2, and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al 2O 3 catalyst are coordinated on the Al 2O 3 support at saturation. When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%. Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3 destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition. 相似文献
14.
Nanoparticles of Ce xZr 1−xO 2 ( x = 0.75, 0.62) were prepared by the oxidation-coprecipitation method using H 2O 2 as an oxidant, and characterized by N 2 adsorption, XRD and H 2-TPR. Ce xZr 1−xO 2 prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of Ce xZr 1−xO 2 increased, but thermal stability of Ce xZr 1−xO 2 decreased. The surface area of Ce 0.62Zr 0.38O 2 was 41.2 m 2/g after calcination in air at 900 °C for 6 h. TPR results showed the formation of solid solution promoted the reduction of CeO 2, and the reduction properties of Ce xZr 1−xO 2 were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce 0.75Zr 0.25O 2 was used as the active washcoat and Pd loading was 0.7 g/L. In the test of Air/Fuel, the conversion of C 3H 8 was close to 100% and NO was completely converted at λ < 1.025. The high conversion of C 3H 8 was induced by the steam reform and dissociation adsorption reaction of C 3H 8. Pd-only catalyst using Ce 0.75Zr 0.25O 2 as active washcoat showed high light off activity, the reaction temperatures ( T50) of 50% conversion of CO, C 3H 8 and NO were 180, 200 and 205 °C, respectively. However, the conversions of C 3H 8 and NO showed oscillation with continuously increasing the reaction temperature. The presence of La 2O 3 in washcoat decreased the light off activity and suppressed the oscillation of C 3H 8 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 La 2O 3 in active washcoat can enhance the thermal stability of catalyst significantly. 相似文献
15.
The role of La 2O 3 loading in Pd/Al 2O 3-La 2O 3 prepared by sol–gel on the catalytic properties in the NO reduction with H 2 was studied. The catalysts were characterized by N 2 physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO. The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La2O3 inclusion. The selectivity depends on the NO/H2 molar ratio (GHSV = 72,000 h−1) and the extent of interaction between Pd and La2O3. At NO/H2 = 0.5, the catalysts show high N2 selectivity (60–75%) at temperatures lower than 250 °C. For NO/H2 = 1, the N2 selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H2O vapor. The high N2 selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdOx phase interacting with La2O3. The formation of this phase is favored by the spreading of PdO promoted by La2O3. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al2O3 the O2 uptake is consistent with the oxidation of PdO to PdO2, and when La2O3 is present the O2 uptake exceeds that amount (1.5 times). La2O3 in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N2. 相似文献
16.
Catalytic performance for partial oxidation of methane (POM) to synthesis gas was studied over the Rh/Al 2O 3 catalysts with Rh loadings between 0.1 and 3 wt%. It was found that the ignition temperature of POM reaction increased with the decreasing of the Rh loadings in the catalysts. For the POM reaction over the catalysts with high (≥1 wt%) Rh loadings, steady-state reactivity was observed. For the reaction over the catalysts with low (≤0.25 wt%) Rh loadings, however, oscillations in CH 4 and reaction products (CO, H 2, and CO 2) were observed. Comparative studies using H 2-TPR, O 2-TPD and high temperature in situ Raman spectroscopy techniques were carried out in order to elucidate the relation between the redox property of the Rh species in the Rh/Al 2O 3 with different Rh loadings and the performance of the catalysts for the reaction. Three kinds of oxidized rhodium species, i.e. the rhodium oxide species insignificantly affected by the support (RhO x), that intimately interacting with the Al 2O 3 surface (Rh iO x) and the Rh(AlO 2) y species formed by diffusion of rhodium oxides in to sublayers of Al 2O 3 [C.P. Hwang, C.T. Yeh, Q.M. Zhu, Catal. Today, 51 (1999) 93.], were identified by H 2-TPR and O 2-TPD experiments. Among them, the first two species can be easily reduced by H 2 at temperature below 350 °C, while the last one can only be reduced by H 2 at temperature above 500 °C. The ignition temperatures of POM reaction over the catalysts are closely related to the temperature at which most of the RhO x and Rh iO x species can be reduced by CH 4 in the reaction mixture. Compared to the Rh/Al 2O 3 with high Rh loadings, the catalysts with low Rh loadings contain more Rh iO x species which possess stronger RhO bond strength and are more difficult to be reduced than RhO x by the reaction mixture. Higher temperature is therefore required to ignite the POM reaction over the catalysts with lower Rh loadings. The oscillation during the POM reaction over the Rh/Al 2O 3 with low Rh loadings can be related to the behaviour of Rh(AlO 2) y species in the catalyst switching cyclically from the oxidized state to the reduced state during the reaction. 相似文献
17.
The effectiveness of Ag/Al 2O 3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al 2O 3, 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, O 2, NO + O 2-temperature programmed desorption (TPD), H 2-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 C 3H 6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C 3H 6 conversion was achieved over Ag/Al 2O 3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al 2O 3 (I) is deemed to be crucial for NO selective reduction into N 2. By contrast, a high C 3H 6 conversion simultaneously with a moderate N 2 yield was observed over Ag/Al 2O 3 (II) prepared from a γ-Al 2O 3 source. The larger particles of Ag mO ( m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al 2O 3 (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 Al 2O 3 (I). A subsequent calcination of Ag/Al 2O 3 (III) at 800 °C led to the generation of Ag/Al 2O 3 (IV) catalyst yielding a significant enhancement in both N 2 yield and C 3H 6 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/Al 2O 3 (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/Al 2O 3 (II and V) > Ag/Al 2O 3 (IV) > Ag/Al 2O 3 (I) > Ag/Al 2O 3 (III) and Al 2O 3 (I). The formation of nitrate species is an important step for the deNO x process, which can be promoted by increasing O 2 feed concentration as evidenced by NO + O 2-TPD study for Ag/Al 2O 3 (I), achieving a better catalytic performance. 相似文献
18.
A series of La(Co, Mn, Fe) 1−x(Cu, Pd) xO 3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N 2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O 2, NO + O 2, C 3H 6, in the absence or presence of 5% H 2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C 3H 6, 1% O 2, 0 or 10% H 2O, and 50,000 h −1 space velocity. The objective was to investigate the influence of H 2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N 2 yield, and 90% C 3H 6 conversion) was achieved at 600 °C over LaFe 0.8Cu 0.2O 3 under a dry feed stream. With the exposure of LaFe 0.8Cu 0.2O 3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N 2 yield, and 86% C 3H 6 conversion. A competitive adsorption between H 2O vapor with O 2 and NO molecules at anion vacancies over LaFe 0.8Cu 0.2O 3 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 C 3H 6 + NO + O 2 reaction. This H 2O deactivation was also verified to be strictly reversible by removing steam from the feed. 相似文献
19.
In this work, a kinetic model is constructed to simulate sulfur deactivation of the NO x storage performance of BaO/Al 2O 3 and Pt/BaO/Al 2O 3 catalysts. The model is based on a previous model for NO x storage under sulfur-free conditions. In the present model the storage of NO x is allowed on two storage sites, one for complete NO x uptake and one for a slower NO x sorption. The adsorption of SO x is allowed on both of these NO x storage sites and on one additional site which represent bulk storage. The present model is built-up of six sub-models: (i) NO x storage under sulfur-free conditions; (ii) SO 2 storage on NO x storage sites; (iii) SO 2 oxidation; (iv) SO 3 storage on bulk sites; (v) SO 2 interaction with platinum in the presence of H 2; (vi) oxidation of accumulated sulfur compounds on platinum by NO 2. Data from flow reactor experiments are used in the implementation of the model. The model is tested for simulation of experiments for NO x storage before exposure to sulfur and after pre-treatments either with SO 2 + O 2 or SO 2 + H 2. The simulations show that the model is able to describe the main features observed experimentally. 相似文献
20.
Performance of NO x traps after high-temperature treatments in different redox environments was studied. Two types of treatments were considered: aging and pretreatment. Lean and rich agings were examined for a model NO x trap, Pt–Ba/Al 2O 3. These were done at 950 °C for 3 h, in air and in 1% H 2/N 2, respectively. Lean aging had a severe impact on NO x trap performance, including HC and CO oxidation, and NH 3 and N 2O formation. Rich aging had minimal impact on performance, compared to fresh/degreened performance. Deactivation from lean aging was essentially irreversible due to Pt sintering, but Pt remained dispersed with the rich aging. Pretreatments were examined for a commercially feasible fully formulated NO x trap and two model NO x traps, Pt–Ba/Al 2O 3 and Pt–Ba–Ce/Al 2O 3. Pretreatments were done at 600 °C for 10 min, and used feed gas that simulated diesel exhaust under several conditions. Lean pretreatment severely suppressed NO x, HC, CO, NH 3 and N 2O activities for the ceria-containing NO x traps, but had no impact on Pt–Ba/Al 2O 3. Subsequently, a relatively mild rich pretreatment reversed this deactivation, which appears to be due to a form of Pt–ceria interaction, an effect that is well known from early work on three-way catalysts. Practical applications of results of this work are discussed with respect to NO x traps for light-duty diesel vehicles. 相似文献
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