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1.
A mean field model, for storage and desorption of NOx in a Pt/BaO/Al2O3 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/Al2O3; (ii) NO oxidation on Pt/BaO/Al2O3; (iii) NOx storage on BaO/Al2O3; (iv) NOx storage on Pt/BaO/Al2O3 with thermal regeneration and (v) NOx storage on Pt/BaO/Al2O3 with regeneration using C3H6. In this paper, we focus on the last sub-system. The kinetic model for NOx storage on Pt/BaO/Al2O3 was constructed with kinetic parameters obtained from the NO oxidation model together with a NOx storage model on BaO/Al2O3. This model was not sufficient to describe the NOx storage experiments for the Pt/BaO/Al2O3, because the NOx desorption in TPD experiments was larger for Pt/BaO/Al2O3, compared to BaO/Al2O3. 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 NOx from Pt/BaO/Al2O3. To this NOx storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO2 and C3H6. The main reactions for continuous reduction of NOx 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.
The reduction of NOx by hydrogen under lean burn conditions over Pt/Al2O3 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 NOx conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al2O3. In this case, although pure H2 and pure CO are ineffective for NOx reduction under lean burn conditions, H2/CO mixtures are very effective. With a realistic (1:3) H2:CO ratio, typical of actual exhaust gas, Pd/Al2O3 is significantly more active than Pt/Al2O3, delivering 45% NOx conversion at 160 °C, compared to >15% for Pt/Al2O3 under identical conditions. The nature of the support is also critically important, with Pd/Al2O3 being much more active than Pd/SiO2. Possible mechanisms for the improved performance of Pd/Al2O3 in the presence of H2+CO are discussed.  相似文献   

3.
In this work, a kinetic model is constructed to simulate sulfur deactivation of the NOx storage performance of BaO/Al2O3 and Pt/BaO/Al2O3 catalysts. The model is based on a previous model for NOx storage under sulfur-free conditions. In the present model the storage of NOx is allowed on two storage sites, one for complete NOx uptake and one for a slower NOx sorption. The adsorption of SOx is allowed on both of these NOx storage sites and on one additional site which represent bulk storage. The present model is built-up of six sub-models: (i) NOx storage under sulfur-free conditions; (ii) SO2 storage on NOx storage sites; (iii) SO2 oxidation; (iv) SO3 storage on bulk sites; (v) SO2 interaction with platinum in the presence of H2; (vi) oxidation of accumulated sulfur compounds on platinum by NO2. Data from flow reactor experiments are used in the implementation of the model. The model is tested for simulation of experiments for NOx storage before exposure to sulfur and after pre-treatments either with SO2 + O2 or SO2 + H2. The simulations show that the model is able to describe the main features observed experimentally.  相似文献   

4.
The behaviour of a Pt(1 wt.%) supported on CeO2–ZrO2(20 wt.%)/Al2O3(64 wt.%)–BaO(16 wt.%) as a novel NOx storage–reduction catalyst is studied by reactivity tests and DRIFT experiments and compared with that of Pt(1%)–BaO(15 wt.%) on alumina. The former catalyst, designed as a hydrothermally stable sample, is composed of an alumina modified with Ba ions and an overlayer of ceria-zirconia. The results pointed out that during the calcination barium ions migrates over the surface of the catalyst which thus show a good NOx storage–reduction behaviour comparable with that of Pt–BaO on alumina, although Ba ions result much better dispersed.  相似文献   

5.
Methane combustion over Pd/Al2O3 catalysts with and without added Pt and CeO2 in both oxygen-rich and methane-rich mixtures at temperatures in the range 250–520°C has been investigated using a temperature-programmed reaction procedure with on-line gas analysis (FTIR). During the temperature loop under oxygen-rich conditions, there was an appreciable hysteresis in the activity of unmodified Pd/Al2O3, which was greatly enhanced over Pd–Pt/Al2O3. Over both catalysts the hysteresis was reversed under slightly methane-rich atmospheres, and as temperature was reduced, a sudden collapse or fluctuations in activity were shown respectively over Pd–Pt/Al2O3 and Pd/Al2O3. Such non-steady behaviour was almost eliminated over Pd/Al2O3–CeO2. Under a very narrow range of conditions and over a Pd/Al2O3 packed bed, oscillation of methane combustion was observed.  相似文献   

6.
Experimental results describing the product distribution during the reduction of NO by H2 on Pt/Al2O3 and Pt/BaO/Al2O3 catalysts are presented in the temperature range 30–500 °C and H2/NO feed ratio range of 0.9–2.5. A microkinetic model that describes the kinetics of NO reduction by H2 on Pt/Al2O3 is proposed and most of the kinetic parameters are estimated from either literature data or from thermodynamic constraints. The microkinetic model is combined with the short monolith flow model to simulate the conversions and selectivities corresponding to the experimental conditions. The predicted trends are in excellent qualitative and reasonable quantitative agreement with the experimental results. Both the model and the experiments show that N2O formation is favored at low temperatures and low H2/NO feed ratios, N2 selectivity increases monotonically with temperature for H2/NO feed ratios of 1.2 or less but goes through a maximum at intermediate temperatures (around 100 °C) for H2/NO feed ratios 1.5 or higher. Ammonia formation is favored for H2/NO feed ratios of 1.5 or higher and intermediate temperatures (100–350 °C) buts starts to decompose at a temperature of 400 °C or higher. The microkinetic model is used to determine the surface coverages and explain the trends in the experimentally observed selectivities.  相似文献   

7.
The NOx storage and reduction functions of a Pt–Ba/Al2O3 “NOx 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 NOx occurs first at BaO and then at BaCO3, which are the most abundant sites following regeneration of catalyst with propylene; (ii) the overall storage process at BaCO3 is slower than at BaO; (iii) CO2 inhibits the NOx storage at low temperatures; (iv) the amount of NOx stored up to catalyst saturation at 350 °C corresponds to 17.6% of Ba; (v) the reduction of stored NOx groups is fast and is limited by the concentration of propylene in the investigated T range (250–400 °C); (vi) selectivity to N2 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   

8.
A systematic mechanistic study of NO storage and reduction over Pt/Al2O3 and Pt/BaO/Al2O3 is carried out using Temporal Analysis of Products (TAP). NO pulse and NO/H2 pump-probe experiments at 350 °C on pre-reduced, pre-oxidized, and pre-nitrated catalysts reveal the complex interplay between storage and reduction chemistries and the importance of the Pt/Ba coupling. NO pulsing experiments on both catalysts show that NO decomposes to major product N2 on clean Pt but the rate declines as oxygen accumulates on the Pt. The storage of NO over Pt/BaO/Al2O3 is an order of magnitude higher than on Pt/Al2O3 showing participation of Ba in the storage even in the absence of gas phase O2. Either oxygen spillover or transient NO oxidation to NO2 is postulated as the first steps for NO storage on Pt/BaO/Al2O3. The storage on Pt/Ba/Al2O3 commences as soon as Pt–O species are formed. Post-storage H2 reduction provides evidence that a fraction of NO is not stored in close proximity to Pt and is more difficult to reduce. A closely coupled Pt/Ba interfacial process is corroborated by NO/H2 pump-probe experiments. NO conversion to N2 by decomposition is sustained on clean Pt using excess H2 pump-probe feeds. With excess NO pump-probe feeds NO is converted to N2 and N2O via the sequence of barium nitrate and NO decomposition. Pump-probe experiments with pre-oxidized or pre-nitrated catalyst show that N2 production occurs by the decomposition of NO supplied in a NO pulse or from the decomposition of NOx stored on the Ba. The transient evolution of the two pathways depends on the extent of pre-nitration and the NO/H2 feed ratio.  相似文献   

9.
The effect of the Pd addition method into the fresh Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts (OSC material = CexZr1−xO2 mixed oxides) was investigated in this study. The CO + NO and CO + NO + O2 model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al2O3) catalyst than for the fresh (Pd + OSC)/Al2O3 catalyst during the CO + NO + O2 reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al2O3) catalyst was higher than that of the (Pd + OSC)/Al2O3 catalyst.  相似文献   

10.
Phase changes in high temperature treated (>900 °C) 8 or 20 wt% BaO supported on γ-Al2O3 model lean NOx trap (LNT) catalysts, induced by NO2 and/or H2O adsorption, were investigated with powder X-ray diffraction (XRD), solid state 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and NO2 temperature programmed desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state 27Al MAS NMR results confirm that stable surface BaO and bulk BaAl2O4 phases are formed for 8 and 20 wt% BaO/Al2O3, respectively. Following NO2 adsorption over these thermally treated samples, some evidence for nanosized Ba(NO3)2 particles are observed in the XRD results, although this may represent a minority phase. However, when water was added to the thermally aged samples after NO2 exposure, the formation of bulk crystalline Ba(NO3)2 particles was observed in both samples. Solid state 27Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO2 TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NOx uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials.  相似文献   

11.
In this study, Pd/Al2O3 and Pd/BaO/Al2O3 metallic monoliths were used to investigate the effect of BaO in C2H4 and CO oxidation as well as in NO reduction. A FT-IR gas analyser was used to study the activity of the catalysts. Several activity experiments carried out with dissimilar feedstreams revealed that BaO enhances CO and C2H4 oxidation as well as NO reduction reactions in rich conditions. This effect is due to BaO, which causes a decrease in the ethene poisoning of palladium. In lean conditions BaO is present in the form of Ba(OH)2 which reacts with oxidised NO releasing water. Therefore, NO was stored during the lean reaction.  相似文献   

12.
Differences in the NOx storage-reduction (NSR) behavior of Pt/Ba/CeO2 and Pt/Ba/Al2O3 have been identified and traced to their different chemical and structural properties. The results show that Pt/Ba/CeO2 exhibits inferior NOx storage and, particularly, reduction (regeneration) activity compared to the Al2O3 supported catalyst. The incomplete reduction of the stored NOx-species in Pt/Ba/CeO2 seems to be caused by a faster and more profound reoxidation of Pt particles during the lean period as evidenced by in situ X-ray absorption spectroscopy. Interestingly, the reduction activity could be significantly improved by a pre-reduction step at mild conditions. Exposure of the Pt/Ba/CeO2 catalyst to reducing H2 atmosphere in the temperature range 300–500 °C lead to a moderate increase of Pt particle size which beneficially influenced the regeneration activity. In contrast, pre-reduction at temperatures above 500 °C was unfavorable and resulted in a severe decrease of the regeneration activity, probably due to migration of the partially reduced CeO2 onto the surface of Pt particles.  相似文献   

13.
通过浸渍法制备了Al_2O_3负载的Pd和Pt催化剂,考察催化剂的甲烷、乙烷和丙烷催化燃烧活性,以及助剂Ba对催化性能的影响。对于Pd/Al_2O_3催化剂,加入Ba使活性物种PdO颗粒变大和还原温度升高,形成更稳定的PdO活性物种,是Pd-Ba/Al_2O_3催化剂活性提升的主要原因。对于Pt/Al_2O_3催化剂,加入Ba助剂使活性物种Pt0含量降低,PtO_x与Al_2O_3载体相互作用增强,使PtO_x物种更难被还原为Pt~0,导致Pt-Ba/Al_2O_3催化剂活性降低。Pd和Pt催化剂催化烷烃氧化反应活性规律一致:丙烷乙烷甲烷。Pd/Al_2O_3催化剂有利于C—H键活化,Pt/Al_2O_3催化剂有利于C—C键活化。Pt/Al_2O_3催化剂对C1-C3烷烃氧化活性的差别明显大于Pd/Al_2O_3催化剂。Pt/Al_2O_3催化剂对碳比例高的烷烃活性更高。  相似文献   

14.
A series of 1 wt.%Pt/xBa/Support (Support = Al2O3, SiO2, Al2O3-5.5 wt.%SiO2 and Ce0.7Zr0.3O2, x = 5–30 wt.% BaO) catalysts was investigated regarding the influence of the support oxide on Ba properties for the rapid NOx trapping (100 s). Catalysts were treated at 700 °C under wet oxidizing atmosphere. The nature of the support oxide and the Ba loading influenced the Pt–Ba proximity, the Ba dispersion and then the surface basicity of the catalysts estimated by CO2-TPD. At high temperature (400 °C) in the absence of CO2 and H2O, the NOx storage capacity increased with the catalyst basicity: Pt/20Ba/Si < Pt/20Ba/Al5.5Si < Pt/10Ba/Al < Pt/5Ba/CeZr < Pt/30Ba/Al5.5Si < Pt/20Ba/Al < Pt/10BaCeZr. Addition of CO2 decreased catalyst performances. The inhibiting effect of CO2 on the NOx uptake increased generally with both the catalyst basicity and the storage temperature. Water negatively affected the NOx storage capacity, this effect being higher on alumina containing catalysts than on ceria–zirconia samples. When both CO2 and H2O were present in the inlet gas, a cumulative effect was observed at low temperatures (200 °C and 300 °C) whereas mainly CO2 was responsible for the loss of NOx storage capacity at 400 °C. Finally, under realistic conditions (H2O and CO2) the Pt/20Ba/Al5.5Si catalyst showed the best performances for the rapid NOx uptake in the 200–400 °C temperature range. It resulted mainly from: (i) enhanced dispersions of platinum and barium on the alumina–silica support, (ii) a high Pt–Ba proximity and (iii) a low basicity of the catalyst which limits the CO2 competition for the storage sites.  相似文献   

15.
The effect of different reducing agents (H2, CO, C3H6 and C3H8) on the reduction of stored NOx over PM/BaO/Al2O3 catalysts (PM = Pt, Pd or Rh) at 350, 250 and 150 °C was studied by the use of both NO2-TPD and transient reactor experiments. With the aim of comparing the different reducing agents and precious metals, constant molar reduction capacity was used during the reduction period for samples with the same molar amount of precious metal. The results reveal that H2 and CO have a relatively high NOx reduction efficiency compared to C3H6 and especially C3H8 that does not show any NOx reduction ability except at 350 °C over Pd/BaO/Al2O3. The type of precious metals affects the NOx storage-reduction properties, where the Pd/BaO/Al2O3 catalyst shows both a high storage and a high reduction ability. The Rh/BaO/Al2O3 catalyst shows a high reduction ability but a relatively low NOx storage capacity.  相似文献   

16.
The deactivation by sulfur and regeneration of a model Pt/Ba/Al2O3 NOx trap catalyst is studied by hydrogen temperature programmed reduction (TPR), X-ray diffraction (XRD), and NOx storage capacity measurements. The TPR profile of the sulfated catalyst in lean conditions at 400 °C reveals three main peaks corresponding to aluminum sulfates (550 °C), “surface” barium sulfates (650 °C) and “bulk” barium sulfates (750 °C). Platinum plays a role in the reduction of the two former types of sulfates while the reduction of “bulk” barium sulfates is not influenced by the metallic phase. The thermal treatment of the sulfated catalyst in oxidizing conditions until 800 °C leads to a stabilization of sulfates which become less reducible. Stable barium sulfides are formed during the regeneration under hydrogen at 800 °C. However, the presence of carbon dioxide and water in the rich mixture allows eliminating more or less sulfides and sulfates, depending on the temperature and time. The regeneration in the former mixture at 650 °C leads to the total recovery of the NOx storage capacity even if “bulk” barium sulfates are still present on the catalyst.  相似文献   

17.
The effect of CeO2 loading (1–20 wt.%) on the properties and catalytic behaviors of CeO2–Al2O3-supported Pt catalysts on the partial oxidation of methane was studied. The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC). XRD and TPR results showed that the pretreatment temperature of the support influences on the amount of CeO2 with fluorite structure. The pretreatment temperature of the support and CeO2 loading influenced the morphology of Pt. OSC analysis showed a significant increase in the oxygen storage capacity per weight of CeO2 for samples with high CeO2 loading (12 and 20 wt.%). TPR analyses showed that the addition of Pt promotes the reduction of CeO2. This effect was more significant for the catalysts with high CeO2 loading (≥12 wt.%). The dispersion of Pt, measured by the rate of cyclohexane dehydrogenation, increases with increasing of the pretreatment temperature of the support. It was shown that the kind of the support is very important for obtaining of catalysts resistant to carbon formation. The catalysts with high CeO2 loading (≥12 wt.%) showed the highest catalytic activity and stability in the reaction of partial oxidation of methane due to a higher Pt–CeO2 interface.  相似文献   

18.
A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 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 H2O and CO2 on NOx storage. The Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is primarily trapped on Al2O3 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 NOx/m2, 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/Al2O3 catalyst are coordinated on the Al2O3 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   


19.
The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO2 (70, 85 wt.%)–Al2O3 (15, 0 wt.%)–WOx (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N2 physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WOx and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO3 bulk phase. The catalysts increased their SBET for about 15% promoted by Al2O3 addition. Various oxidation states of WOx species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WOx species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W6+ and reduced-state WOx species (either W4+ or W0). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.  相似文献   

20.
Oxidation of propene and propane to CO2 and H2O has been studied over Au/Al2O3 and two different Au/CuO/Al2O3 (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co3O4/Al2O3 (4.1 wt.% Au) and Pt/Al2O3 (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO).

A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al2O3 is almost as active as Pt/Al2O3, whereas Au/Co3O4/Al2O3 performs less than any of the CuO-containing gold-based catalysts.

The light-off temperature for C3H8 oxidation is significantly higher than for C3H6. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al2O3 (gold particles less than 3 nm) and 4Au/Co3O4/Al2O3 (gold particles less than 5 nm).  相似文献   


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