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1.
A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NOx adsorber catalyst, Pt/K/Al2O3, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al2O3 phase with associated hydroxyl groups at the surface, and an alkalized-Al2O3 phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al2O3 and 65% for the alkalized-Al2O3. NO2 and CO2 chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al2O3 adsorbs 0.087 μmol CO2/m2and 2.0 μmol NO2/m2, and Pt/K/Al2O3 adsorbs 2.0 μmol CO2/m2and 6.4 μmol NO2/m2. This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al2O3 during both lean and rich periods of the NOx adsorber catalyst cycle.  相似文献   

2.
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   

3.
Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst   总被引:1,自引:0,他引:1  
Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al2O3 catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al2O3 catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h−1. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 1017 s−1.  相似文献   


4.
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   

5.
In this paper, the effect of CO2 and H2O on NOx storage and reduction over a Pt–Ba/γ-Al2O3 (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO2 and H2O, NOx is stored on BaCO3 sites only. Moreover, H2O inhibits the NO oxidation capability of the catalyst and no NO2 formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N2 as well as complete regeneration of stored NO. In the presence of CO2, NO is oxidized into NO2 and more NOx is stored as in the presence of H2O, resulting in 30% barium utilization. Bulk barium sites are inactive in NOx trapping in the presence of CO2·NH3 formation is seen in the rich phase and the selectivity towards N2 is 83%. Ba(NO3)2 is always completely regenerated during the subsequent rich phase. In the absence of CO2 and H2O, both surface and bulk barium sites are active in NOx storage. As lean/rich cycling proceeds, the selectivity towards N2 in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NOx storage.  相似文献   

6.
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   

7.
The presence of sulfur in automotive exhaust is known to be detrimental to lean-NOx traps as SO2 is oxidized to SO3 that competes with NO2 for sites on the trap and is difficult to remove. In this study the effect of adding Cu to the prototypical Pt–BaO/γ-Al2O3 formulation on the system's tolerance for sulfur was investigated. It was found that in the absence of sulfur, Cu decreases the performance in terms of both NOx storage capacity and reduction of NOx to N2 during regeneration. In the presence of SO2, Cu provides a significant improvement in sulfur tolerance so that, after sulfur exposure, the storage capacity of the Cu-modified material can exceed that of the baseline material. The sulfur tolerance afforded by Cu is attributed to a moderation in the activity for SO2 oxidation resulting from the formation of a Pt–Cu bimetallic phase. The propensity for NO oxidation is also modified, but to a lesser effect. Evidence for the bimetallic phase is provided by temperature-programmed reduction (TPR) and electron microscopy. The impact of SO2 on the Cu-modified material is greater during the regenerative reduction cycle. In this case, the results suggest that sulfur blocks Pt and possibly Cu sites and that the sulfur is not removed by oxidation during the subsequent storage cycle. Hence, activity lost during the reduction cycle is not restored. In contrast, sulfur that blocks Pt sites on the baseline material during the reduction cycle is subsequently oxidized and desorbs from the Pt, restoring the activity. However, some of the resulting SO3 reacts with the BaO to form BaSO4, and there is a partial loss of storage capacity.  相似文献   

8.
This study addresses the catalytic reaction of NOx and soot into N2 and CO2 under O2-rich conditions. To elucidate the mechanism of the soot/NOx/O2 reaction and particularly the role of the catalyst -Fe2O3 is used as model sample. Furthermore, a series of examinations is also made with pure soot for reference purposes. Temperature programmed oxidation and transient experiments in which the soot/O2 and soot/NO reaction are temporally separated show that the NO reduction occurs on the soot surface without direct participation of the Fe2O3 catalyst. The first reaction step is the formation of CC(O) groups that is mainly associated with the attack of oxygen on the soot surface. The decomposition of these complexes leads to active carbon sites on which NO is adsorbed. Furthermore, the oxidation of soot by oxygen provides a specific configuration of active carbon sites with suitable atomic orbital orientation that enables the chemisorption and dissociation of NO as well as the recombination of two adjacent N atoms to evolve N2. Moreover, carbothermal reaction, high resolution transmission electron microscopy and isotopic studies result in a mechanistic model that describes the role of the Fe2O3 catalyst. This model includes the dissociative adsorption of O2 on the iron oxide, surface migration of the oxygen to the contact points of soot and catalyst and then final transfer of O to the soot. Moreover, our experimental data suggest that the contact between both solids is maintained up to high conversion levels thus resulting in continuous oxygen transfer from catalyst to soot. As no coordinative interaction of soot and Fe2O3 catalyst is evidenced by diffuse reflectance infrared Fourier transform spectroscopy a van der Waals type interaction is supposed.  相似文献   

9.
The phase diagram of the Al2O3–ZrO2–Nd2O3 system was constructed in the temperature range 1250–2800 °C. The liquidus surface of the phase diagram reflects the preferentially eutectic interaction in the system. Two new ternary and one new binary eutectics were found. The minimum melting temperature is 1675 °C and it corresponds to the ternary eutectic Nd2O3·11Al2O3 + F-ZrO2 + NdAlO3. The solidus surface projection and the schematic of the alloy crystallization path confirm the preferentially congruent character of phase interaction in the ternary system. The polythermal sections present the complete phase diagram of the Al2O3–ZrO2–Nd2O3 system. No ternary compounds or regions of remarkable solid solution were found in the components or binaries in this ternary system.  相似文献   

10.
K. Vaezzadeh  C. Petit  V. Pitchon   《Catalysis Today》2002,73(3-4):297-305
NOx sorption and reduction capacities of 12-tungstophosphoric acid hexahydrate (H3PW12O40·6H2O, HPW) were measured under representative alternating conditions of lean and rich exhaust-type gas mixture. Under lean conditions, the sorption of NOx is large and is equivalent to 37 mg of NOx/gHPW. Although a part of these NOx remains unreduced, HPW is able to reduce some of the NOx to produce N2 by a reaction between the sorbed NO2 and hydrocarbon (HC), but this process is slow. The addition of 1% Pt affects strongly the chemical behaviour occurring during the course of a rich operation. The NO desorption observed at the beginning of the rich phase is strongly accelerated. The direct correlation between NO2 consumption and CO2 production shows that the principal pathway is the reaction CO+NO2→CO2+NO. In a mixture of reducing gas (CO, HC, H2), the competition is strongly in favour of CO though in its absence the reaction observed was the hydrogenation of propene to propane.  相似文献   

11.
The sulphur tolerance and thermal stability of a 2 wt% Ag/γ-Al2O3 catalyst was investigated for the H2-promoted SCR of NOx with octane and toluene. The aged catalyst was characterised by XRD and EXAFS analysis. It was found that the effect of ageing was a function of the gas mix and temperature of ageing. At high temperatures (800 °C) the catalyst deactivated regardless of the reaction mix. EXAFS analysis showed that this was associated with the Ag particles on the surface of the catalyst becoming more ordered. At 600 and 700 °C, the deactivating effect of ageing was much less pronounced for the catalyst in the H2-promoted octane-SCR reaction and ageing at 600 °C resulted in an enhancement in activity for the reaction in the absence of H2. For the toluene + H2-SCR reaction the catalyst deactivated at each ageing temperature. The effect of addition of low levels of sulphur (1 ppm SO2) to the feed was very much dependent on the reaction temperature. There was little deactivation of the catalyst at low temperatures (≤235 °C), severe deactivation at intermediate temperatures (305 and 400 °C) and activation of the catalyst at high temperatures (>500 °C). The results can be explained by the activity of the catalyst for the oxidation of SO2 to SO3 and the relative stability of silver and aluminium sulphates. The catalyst could be almost fully regenerated by a combination of heating and the presence of hydrogen in the regeneration mix. The catalyst could not be regenerated in the absence of hydrogen.  相似文献   

12.
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   

13.
冉雷  陈希慧 《工业催化》2013,21(7):45-48
对柠檬醛-乙酸乙酯溶液中柠檬醛在La2O3/γ-Al2O3催化剂上等温吸附行为进行了研究。结果表明,30 ℃柠檬醛在La2O3/γ-Al2O3催化剂上的吸附动力学符合准二阶吸附动力学模型,吸附动力学方程为:1/qt=2.350/t+0.063 3(R2=0.998 5)。(30~65) ℃柠檬醛在La2O3/γ-Al2O3催化剂上的等温吸附符合Langmuir方程,温度升高使柠檬醛的饱和吸附量增加,吸附热为32.19 kJ·mol-1。  相似文献   

14.
Pt–xMo/γ-Al2O3 catalysts of different molybdenum loading (2–20 wt.%) and with 1 wt.% of platinum were prepared by successive wet impregnation after intermediate calcination. The structure, morphology and surface were characterized by various methods. The DRS results indicate the presence of octahedral Mo6+ and tetrahedral Mo6+ phases. It also evidences the presence of polymeric MoOx species, responsible for the formation of a well dispersed surface sublayer and bulk MoO3 crystalline phase. XPS results after reduction and passivation of the 1Pt and 1Pt2Mo revealed the presence of residual chlorine, in the form of surface species such as [Pt(OH)xCly]s and [PtOxCly]sfavoring the formation of well dispersed platinum particles. The TPD and FTIR results are consistent with the existence of new active sites of Pt in the presence of molybdenum loading. For low Mo content there is a H2 spillover effect. These results confirm the decoration model of Pt encapsulation by partially reduced Mo species as well as H2 storage and backspillover due to the generation of a bronze compound.  相似文献   

15.
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   

16.
The performance of Ir/γ-Al2O3 catalyst for the decomposition of high concentration hydrogen peroxide was investigated in a monopropellant thruster. The changes of ignition delay (t0), chamber pressure (Pc) and catalyst bed temperature (Tc) with the numbers of startup–shutdown cycles were proved to be effective indicators of catalyst bed efficiency. The fresh catalyst and the deactivated catalyst were characterized with H2-TPR, XRD and XPS. It was found that catalyst oxidation and surface Sn poisoning are the major reasons of catalyst deactivation.  相似文献   

17.
The role of ozone was studied for two different configurations combining non-thermal plasma (NTP) and heterogeneous catalysis, namely the use of a gas phase plasma with subsequent exposure of the effluent to a catalyst in a packed-bed reactor (post-plasma treatment) and the placement of the catalyst directly in the discharge zone (in-plasma catalysis). Non-porous and porous alumina and silica were deployed as model catalysts. The oxidation of immobilised hydrocarbons, toluene as a volatile organic compound and CO as an inorganic pollutant were studied in both operational modes.

While conversion and selectivity of hydrocarbon oxidation in the case of catalytic post-plasma treatment can be fully explained by the catalytic decomposition of O3 on γ-Al2O3, the conversion processes for in-plasma catalysis are more complex and significant oxidation was also measured for the other three materials (-Al2O3, quartz and silica gel). It became obvious that additional synergetic effects can be utilised in the case of in-plasma catalysis due to short-lived species formed in the NTP.

The capability of porous alumina for ozone decomposition was found to be correlated with its activity for oxidation of carbon-containing agents. It could be clearly shown that the reaction product CO2 poisons the catalytic sites at the γ-Al2O3 surface. The catalytic activity for O3 decomposition can be partially re-established by NTP treatment. However, for practical purposes the additional reaction pathways provided by in-plasma catalytic processes are essential for satisfactory conversion and selectivity.  相似文献   


18.
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   

19.
This study provides insight into the effect of Pt dispersion on the overall rate and product distribution during NOx storage and reduction. The storage and reduction performance of Pt/BaO/A2O3 monoliths with varied Pt dispersion (3%, 8%, and 50%) and fixed Pt (2.48 wt.%) and BaO (13.0 wt.%) loadings is reported. At low temperature (<200 °C), the differences in storage and reduction activity were the largest between the three catalysts. The amount of NOx stored increased with increased dispersion, as did the amount of stored NOx that was reduced. These trends are attributed to larger Pt surface area and Pt–BaO interfacial perimeter, the latter of which enhances the spillover of surface species between the precious metal and storage components. At high temperature (370 °C), the stored NOx was almost completely regenerated for the three catalysts. However, the regeneration of the 3% dispersion catalyst was much slower, suggesting a rate limitation involving the reverse spillover of stored NOx to Pt and/or of adsorbed hydrogen from Pt to BaO. The results indicate that the catalyst dispersion and operating conditions may be tuned to achieve the desired ammonia selectivity. For the aerobic regeneration feed, the most (net) NH3 was generated by the 50% dispersion catalyst at the lowest temperature (125 °C), by the 3% dispersion catalyst at the highest temperature (340 °C), and by the 8% dispersion catalyst at the intermediate temperatures (170–290 °C). Similar trends were observed for the net production of NH3 with an anaerobic regeneration feed. A phenomenological picture is proposed that describes the effects of Pt dispersion consistent with the established spatio-temporal behavior of the lean NOx trap.  相似文献   

20.
通过制备高纯度的前驱体湃铝石获得了η-Al2O3材料,采用XRD验证了η-Al2O3与γ-Al2O3在晶相结构上的差异,比较了两者的表面形貌、织构及酸碱性能,结果显示,η-Al2O3与γ-Al2O3的比表面积相当,但η-Al2O3具有更弱的弱碱位和较少的强碱位,并拥有丰富的中等强度酸性位。将η-Al2O3与γ-Al2O3作为催化剂应用于CS2水解反应,结果表明,在(200~450) ℃测试温度范围内,η-Al2O3催化剂对CS2的水解活性始终优于γ-Al2O3,两种催化剂上CS2反应的浓度效应也明显不同,推测与它们的酸碱性质影响了对CS2的吸附能力有关,导致两者催化CS2水解反应遵循了不同的机制。  相似文献   

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