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1.
Catalytic activity of H- and FeH-ferrierite (FER) zeolites with iron content from 50 to 4000 ppm in NO–NO2 equilibration and SCR of NOx by propane was measured, both in NO2-poor and NO2-rich streams. The activity of FeH-FER in SCR in NO2-poor streams depends strongly on the Fe content; this relationship is valid down to traces of iron, while no such correlation was indicated in NO2-rich streams. This was rationalized by realizing the negligible activity of zeolite protons for NO–NO2 equilibration. Accordingly the SCR activity of H-FER in NO2-poor streams necessitates presence of iron traces. In the NO2–O2–propane mixtures a process in absence of zeolite catalyst initiating propane oxidation and NO2→NO conversion, but without N2 formation, was evidenced at temperatures over 350 °C. It is suggested that such a radical process participate in characteristic narrow temperature window for NOx reduction by propane.  相似文献   

2.
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   

3.
Characteristics of MnOy–ZrO2 and Pt–ZrO2–Al2O3 as reversible sorbents of NOx were investigated under dynamic changes in atmosphere. These sorbents can be used reversibly with a change of C3H8 concentration in the reaction gases. Catalytic reduction of NO occurred in the presence of propane, which was more pronounced on Pt–ZrO2–Al2O3 than on MnOy-ZrO2 due to high activity of Pt surface for this reaction on MnOy in MnOy–ZrO2. The sorption was observed as soon as the atmosphere changed from a reducing to an oxidizing one. This implies that a high equilibrium partial pressure of O2 is necessary for NO uptake since the sorbed NO3 species becomes stable. The beginning of NOx desorption atmospheres was somewhat dependent on the amount of stored NOx. The presence of propane in the gas phase strongly affected the characteristic sorption and desorption properties of MnOy–ZrO2 and Pt–ZrO2–Al2O3. The sorption and desorption properties are different for MnOy–ZrO2 and Pt–ZrO2–Al2O3, since the noble metal or metal oxide possesses unique activity for the NO reaction with C3H8 and the amount of oxygen available for oxidative sorption of NO.  相似文献   

4.
On an anodic alumina supported silver catalyst with a low Ag loading (1.68 wt.%), NOx (NO/He, NO/O2/He, NO2/He) adsorption measurements and NOx-temperature programmed decomposition (TPD)/temperature programmed surface-reaction (TPSR) measurements in different gas streams (He, C3H6/He, C3H6/O2/He) were conducted to investigate the formation, consumption and reactivity of surface adsorbed NOx species.

During NO adsorption, no noticeable uptake of NO was detected. Introducing oxygen greatly improved the formation of ads-NOx species. A greater quantity of surface nitrate species was found after NO2 adsorption, accompanied with gaseous NO release. The result of TPSR demonstrates the surface nitrate species can be effectively and preferentially reduced by propene. When introducing oxygen into the propene gas stream of TPSR test, the significantly increased amount of reacted nitrate undoubtedly shows the importance of oxygen in activating propene. The pathway for the selective reduction of NOx in the presence of excess oxygen is proposed to pass through the selective reduction of the adsorbed nitrate species with the activated propene.

The enhanced NOx conversion when replacing NO with NO2 was attributed to the stronger NOx adsorption capacity and oxidation ability of NO2, than those for NO. With increasing oxygen concentration, the difference between NO and NO2 would gradually decrease, and finally disappear in a high excess of oxygen.  相似文献   


5.
Kinetic and in situ spectroscopic studies of Co–Pt/MFI and Co–Pt/HY catalysts for the selective reduction of NOx with propylene in the presence of oxygen were carried out. The results of catalytic tests of Co–Pt/MFI showed that the addition of Pt to Co based catalyst improved the activity, but a small increase in selectivity to N2O (15–20%) was observed. In the case of Co–Pt/HY catalyst, the addition of Pt improved the activity more significantly and however, a larger increase in selectivity to N2O (6–72%) was obtained. It was also found from the results of FT-IR studies of Co–Pt/MFI that the reduction of NO to N2 was as follows: firstly the oxidation of NO to NO2 occurred over metallic Pt and NO2 forms Co–NO2, Co–ONO, and/or Co–ONO2; secondly, the partial oxidation of C3H6 was happened over Brønsted acid sites and the reaction of NO2 formed on Co sites with partial oxidized C3H6 produced organo-nitro species. These species were dehydrated and isomerized to form isocyanate. Finally, [NCO] type intermediates react with NO from gas phase to selectively yield N2.  相似文献   

6.
The selective catalytic reduction (SCR) of NOx assisted by propene is investigated on Pd/Ce0.68Zr0.32O2 catalysts (Pd/CZ), and is compared, under identical experimental conditions, with that found on a Pd/SiO2 reference catalyst. Physico-chemical characterisation of the studied catalysts along with their catalytic properties indicate that Pd is not fully reduced to metallic Pd for the Pd/CZ catalysts. This study shows that the incorporation of Pd to CZ greatly promotes the reduction of NO in the presence of C3H6. These catalysts display very stable deNOx activity even in the presence of 1.7% water, the addition of which induces a reversible deactivation of about 10%. The much higher N2 selectivity obtained on Pd/CZ suggests that the lean deNOx mechanism occurring on these catalysts is different from that occurring on Pd0/SiO2. A detailed mechanism is proposed for which CZ achieves both NO oxidation to NO2 and NO decomposition to N2, whereas PdOx activates C3H6 via ad-NO2 species, intermediately producing R-NOx compounds that further decompose to NO and CxHyOz. The role of the latter oxygenates is to reduce CZ to provide the catalytic sites responsible for NO decomposition. The proposed C3H6-assisted NO decomposition mechanism stresses the key role of NO2, R-NOx and CxHyOz as intermediates of the SCR of NOx by hydrocarbons.  相似文献   

7.
Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH4 and C3H8, in order to investigate the effect of the concentration of the fuels, O2 and H2O on NOx emission and combustion characteristics. Among the hexaaluminate catalysts, Sr0.8La0.2MnAl11O19− prepared by the alkoxide method exhibited the highest activity for methane combustion and low NOx emission capability. NOx emission at 1500 °C was increased linearly with O2 concentration, whereas water vapor addition decreased NOx emission in CH4 combustion over the Sr0.8La0.2MnAl11O19− catalyst. In the catalytic combustion of C3H8 over the Sr0.8La0.2MnAl11O19− catalyst, the amount of NOx emitted was raised in the temperature range between 1000 and 1500 °C when the C3H8 concentration increased from 1 to 2 vol.%. It was found that NOx emission in this temperature range was reduced effectively by adding water vapor.  相似文献   

8.
The selective catalytic reduction of NOx by methane on noble metal-loaded sulfated zirconia (SZ) catalysts was studied. Ru, Rh, Pd, Ag, Ir, Pt, and Au-loaded sulfated zirconia catalysts were compared with the intact sulfated zirconia. For the NO–CH4–O2 reaction, Ru, Rh, Pd, Ir, and Pt showed promotion effect on NOx reduction, while for the NO2–CH4–O2 reaction, only Rh and Pd showed promotion effect. Over intact and Rh, Pd, Ag, and Au-loaded sulfated zirconia, NOx conversion in NO2–CH4–O2 reaction was significantly higher than that in NO–CH4–O2 reaction, while clear difference was not observed over Ru, Ir, and Pt-loaded sulfated zirconia. Comparison of [NO2]/([NO]+[NO2]) in the effluent gases in NO–O2 and NO2–O2 reactions showed that Ru, Ir, and Pt has high activity for NO oxidation under the reaction conditions. These facts suggest that effects of these metals toward NOx reduction by methane can be categorized into the following three groups: (i) low activity for NO oxidation to NO2, and high activity for NO2 reduction to N2 (Pd, Rh); (ii) high activity for NO oxidation to NO2, and low activity for NO2 reduction to N2 (Ru, Ir, Pt); (iii) low activity for both reactions (Ag, Au). To confirm these suggestions, combination of these metals were investigated on binary or physically-mixed catalysts. The combination of Pd or Rh with Pt or Ru gave high activity for the selective reduction of NOx by methane.  相似文献   

9.
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   

10.
The catalytic activity of tungstophosphoric acid and Pt loaded MCM-41 for the catalytic reduction of NOx with propene in the presence of water vapor was studied. Pt/MCM-41 was found to be most active, the loading with H3PW12O40 led to an improved selectivity to N2 formation and to an enhanced activity in the presence of water vapor. Hydrated tungstophosphoric acid generated additional sorption sites for C3H6 and led to a higher local concentration of the reducing agent on the catalyst surface, which was found to increase the activity of the Pt and H3PW12O40 loaded catalysts in the presence of water vapor.  相似文献   

11.
This paper deals with the activity of bimetallic potassium–copper and potassium–cobalt catalysts supported on alumina for the reduction of NOx with soot from simulated diesel engine exhaust. The effect of the reaction temperature, the soot/catalyst mass ratio and the presence of C3H6 has been studied. In addition, the behavior of two monometallic catalysts supported on zeolite beta (Co/beta and Cu/beta), previously used for NOx reduction with C3H6, as well as a highly active HC-SCR catalyst (Pt/beta) has been tested for comparison. The preliminary results obtained in the absence of C3H6 indicate that, at temperatures between 250 and 400 °C, the use of bimetallic potassium catalysts notably increases the rate of NOx reduction with soot evolving N2 and CO2 as main reaction products. At higher temperatures, the catalysts mainly favor the direct soot combustion with oxygen. In the presence of C3H6, an increase in the activity for NOx reduction has been observed for the catalyst with the highest metal content. At 450 °C, the copper-based catalysts (Cu/beta and KCu2/Al2O3) show the highest activity for both NOx reduction (to N2 and CO2) and soot consumption. The Pt/beta catalyst does not combine, at any temperature, a high NOx reduction with a high soot consumption rate.  相似文献   

12.
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   

13.
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   

14.
The mechanism of the NO/C3H6/O2 reaction has been studied on a Pt-beta catalyst using transient analysis techniques. This work has been designed to provide answers to the volcano-type activity behaviour of the catalytic system, for that reason, steady state transient switch (C3H6/NO/O2 → C3H6/Ar/O2, C3H6/Ar/O2 → C3H6/NO/O2, C3H6/NO/O2 → Ar/NO/O2, Ar/NO/O2 → C3H6/NO/O2, C3H6/NO/O2 → C3H6/NO/Ar and C3H6/NO/Ar → C3H6/NO/O2) and thermal programmed desorption (TPD) experiments were conducted below and above the temperature of the maximum activity (Tmax). Below Tmax, at 200 °C, a high proportion of adsorbed hydrocarbon exists on the catalyst surface. There exists a direct competition between NO and O2 for Pt free sites which is very much in favour of NO, and therefore, NO reduction selectively takes place over hydrocarbon combustion. NO and C3H6 are involved in the generation of partially oxidised hydrocarbon species. O2 is essential for the oxidation of these intermediates closing the catalytic cycle. NO2 is not observed in the gas phase. Above Tmax, at 230 °C, C3H6 ads coverage is negligible and the surface is mainly covered by Oads produced by the dissociative adsorption of O2. NO2 is observed in gas phase and carbon deposits are formed at the catalyst surface. From these results, the state of Pt-beta catalyst at Tmax is inferred. The reaction proceeds through the formation of partially oxidised active intermediates (CxHyOzNw) from C3H6 ads and NOads. The combustion of the intermediates with O2(g) frees the Pt active sites so the reaction can continue. Temperature has a positive effect on the surface reaction producing active intermediates. On the contrary, formation of NOads and C3H6 ads are not favoured by an increase in temperature. Temperature has also a positive effect on the dissociation of O2 to form Oads, consequently, the formation of NO2 is favoured by temperature through the oxygen dissociation. NO2 is very reactive and produces the propene combustion without NO reduction. These facts will determine the maximum concentration of active intermediates and consequently the maximum of activity.  相似文献   

15.
Transient behaviour of catalytic monolith converter with NOx storage is studied under conditions typical for automobiles with lean-burn engines (i.e., diesel and advanced gasoline ones). Periodical alternation of inlet concentrations is applied—NOx are adsorbed on the catalyst surface during a long reductant-lean phase (2–3 min) and then reduced to N2 within a short reductant-rich phase (2–6 s). Samples of industrial NOx storage and reduction catalyst of NM/Ba/CeO2/γ-Al2O3 type (NM = noble metal), washcoated on 400 cpsi cordierite substrate, are used in the study. Effects of the rich-phase length and composition on the overall NOx conversions are examined experimentally. Reduction of NOx by CO, H2 and unburned hydrocarbons (represented by C3H6) in the presence of CO2 and H2O is considered.

Effective, spatially 1D, heterogeneous mathematical model of catalytic monolith with NOx and oxygen storage capacity is described. The minimum set of experiments needed for the evaluation of relevant reaction kinetic parameters is discussed: (i) CO, H2 and HC oxidation light-off under both lean and rich conditions, including inhibition effects, (ii) NO/NO2 transformation, (iii) NOx storage, including temperature dependence of effective NOx storage capacity, (iv) water gas shift and steam reforming under rich conditions, i.e., in situ production of hydrogen, (v) oxygen storage and reduction, including temperature dependence of effective oxygen storage capacity, and (vi) NOx desorption and reduction under rich conditions. The experimental data are compared with the simulation results.  相似文献   


16.
Pt-based catalysts have been prepared using supports of different nature (γ-Al2O3, ZSM-5, USY, and activated carbon (ROXN)) for the C3H6-SCR of NOx in the presence of excess oxygen. Nitrogen adsorption at 77 K, pH measurements, temperature-programmed desorption of propene, and H2 chemisorption were used for the characterization of the different supports and catalysts. The performance of these catalysts has been compared in terms of de-NOx activity, hydrocarbon adsorption and combustion at low temperature, and selectivity to N2. Maximum NOx 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/Al2O3. 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 NOx reduction. The support play an important role in the reaction mechanism through the hydrocarbon activation. N2O formation was observed for all the catalysts. N2 selectivity ranges from 15 to 30% with the order, Pt/ROXN>Pt-USYPt/Al2O3>Pt-ZSM-5. The catalytic systems exhibit a stable operation under isothermal conditions during time-on-stream experiments.  相似文献   

17.
Preliminary studies on a series of nanocomposite BaO–Fe ZSM-5 materials have been carried out to determine the feasibility of combining NOx trapping and SCR-NH3 reactions to develop a system that might be applicable to reducing NOx emissions from diesel-powered vehicles. The materials are analysed for SCR-NH3 and SCR-urea reactivity, their NOx trapping and NH3 trapping capacities are probed using temperature programmed desorption (TPD) and the activities of the catalysts for promoting the NH3 ads + NO/O2 → N2 and NOx ads + NH3 → N2 reactions are studied using temperature programmed surface reaction (TPSR).  相似文献   

18.
The selective catalytic reduction (SCR) of nitrogen oxides (NOx) by propane in the presence of H2 on sol–gel prepared Ag/Al2O3 catalysts (0.5–5 wt.% Ag) was investigated. It was confirmed that hydrocarbon-assisted SCR of NOx is remarkably enhanced by co-feeding hydrogen to a lean exhaust gas mixture (λ>1), attaining considerable activity within a wide temperature window (470–825 K). The samples had marginal activity at 575 K without co-fed H2, but achieved up to 60% NOx conversion in the presence of H2 at a space velocity of 30,000 h−1. NO2 as NOx feed component is not converted to N2 by C3H8 to a substantial extent under lean conditions. This points to an activation route of NO through direct conversion to adsorbed nitrite/nitrate or to a dissociation of NO over Ag0, formed through short-term reduction by H2. The nature of Ag species was characterized by X-ray diffraction, temperature-programmed reduction, pulse thermoanalytical measurements, electron microscopy and FTIR spectroscopy. It could be shown that Ag2O nano-sized clusters are predominantly present on all samples, whereas formation of silver aluminate could not be confirmed. Nano-sized Ag2O clusters can reversibly be reduced/reoxidized by H2. A silver loading higher than 2 wt.% leads to a part of Ag2O particles, which are thermally decomposed during calcination at 800 K or higher. The catalytic role of this metallic silver is still unclear. Formal kinetic analysis of catalytic data revealed that the activation energy of the overall reaction is significantly lowered in the presence of H2. The presence of water does not change the activation energy. It is concluded that hydrogen reduces the nano-sized Ag2O clusters to Ag0 on a short-term scale. Zero-valent silver promotes a dissociation pathway of NOx conversion. The fact that more oxidized ad-species (nitrite/nitrate) are observed in the presence of H2 is attributed to a dissociative activation of gas-phase oxygen on Ag0.  相似文献   

19.
Investigation of the mechanism of the selective reduction of NOx by propane over the individual samples of commercial catalysts NTK, STK, and Ni–Cr-oxide catalyst and over their binary mechanical mixtures has shown that the synergistic effect observed in the latter case is caused by the oxidative activation of propane on the STK and Ni–Cr-oxide surface which results in the formation of more effective reducing agents, propylene and hydrogen correspondingly. In the case of the Ni–Cr-oxide and NTK catalytic system, hydrogen forms over the former catalyst in propane oxidation, migrates through the gas phase to the latter catalyst, where NOx is activated with the formation of nitrate structures which interact with the said hydrogen giving the products of the overall reaction, N2 and H2O. When the pair of NTK and STK is concerned, the interaction of C3H8 and O2 over the latter catalyst gives stable products of partial propane oxidation and/or oxidative dehydrogenation which are transported due to interphase diffusion to NTK surface. The nature of observed synergistic enhancement of catalysis in the case of binary mixtures is proposed under the terms of “remote control” mechanism described in literature and can serve a useful purpose in the design of catalysts for this reaction.  相似文献   

20.
The selective reduction of NOx over H-mordenite (H-m) was studied using CH3OH as reducing agent. Results are compared with those obtained with other conventional reducing agents (ethylene and methane), with gas-phase reactions, and with other metal-exchanged mordenites (Cu-mordenite (Cu-m) and Co-mordenite (Co-m)). H-m was found to be an effective catalyst for the SCR of NOx with CH3OH. When different reducing agents were compared over H-m, CH3OH > C2H4 > CH4 was the order according to the maximum NO conversion obtained using 1% of oxygen in the feed. Instead, if selectivity is considered, the order results CH4 > CH3OH > C2H4. In reaction experiments, two distinct zones defined by two maxima with NO to N2 conversion are obtained at two different temperatures. A correlation exists between the said zones and the CO : CO2 ratio. At low temperatures, CO prevails whereas at high temperatures CO2 prevails. These results indicate that there exist different reaction intermediates. Evidence from reaction experiments, FTIR results, and transient experiments suggest that the reaction mechanism involves formaldehyde and dimethyl ether (DME) as intermediates in the 200–500°C temperature range. The surface interaction between CH3OH (or its decomposition products) and NO is negligible if compared with NO2, indicating that the oxidation of NO to NO2 on acid sites is a fundamental path in this system. Different from other non-oxygenated reductants (methane and ethylene), a gas-phase NOx initiation effect on hydrocarbon combustion was not observed.  相似文献   

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