共查询到20条相似文献,搜索用时 15 毫秒
1.
A comparison study was carried out on non-thermal plasma (NTP)-assisted selective catalytic reduction (SCR) of NOx by propene over Ag/USY and Ag/Al2O3 catalysts. Ag/USY was almost inactive in thermal SCR while it showed obvious activities in NTP-assisted SCR at 100 °C–200 °C. Although the NOx conversion over Ag/Al2O3 was also enhanced at 300 °C–400 °C by the assistance of NTP, it was ineffective below 250 °C. The intermediates over Ag/USY and Ag/Al2O3 were investigated using in situ DRIFTS method. It was found that key intermediates in HC-SCR, such as NCO, CN, oxygenates and some N-containing organic species were enriched after the assistance of NTP. The differences in the behaviors of above intermediates were not found between these two kinds of catalysts. However, some evidences suggested that different properties of the absorbed NOx species resulted in the distinction of SCR reactions over Ag/USY and Ag/Al2O3. TPD profiles of Ag/Al2O3 showed that nitrates formed over the catalyst were quite stable at low temperatures, which might occupy the active sites and were unfavorable to SCR reactions. The nitrates over Ag/USY were unstable, among which the unidentate nitrate species is probably contributed to the SCR reactions at low temperatures. 相似文献
2.
The selective catalytic reduction (SCR) of NO by C3H6 in excess oxygen was evaluated and compared over Ag/Al2O3 and Cu/Al2O3 catalysts. Ag/Al2O3 showed a high activity for NO reduction. However, Cu/Al2O3 showed a high activity for C3H6 oxidation. The partial oxidation of C3H6 gave surface enolic species and acetate species on the Ag/Al2O3, but only an acetate species was clearly observed on the Cu/Al2O3. The enolic species is a more active intermediate towards NO + O2 to yield—NCO species than the acetate species on the Ag/Al2O3 catalyst. The Ag and Cu metal loadings and phase changes on Al2O3 support can affect the activity and selectivity of Ag/Al2O3 and Cu/Al2O3 catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al2O3 catalyst for NO reduction is higher than that of the Cu/Al2O3 catalyst. 相似文献
3.
M. Richter U. Bentrup R. Eckelt M. Schneider M. -M. Pohl R. Fricke 《Applied catalysis. B, Environmental》2004,51(4):261-274
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
4.
The adsorption and transformation of ammonia over V2O5, V2O5/TiO2, V2O5-WO3/TiO2 and CuO/TiO2 systems has been investigated by FT-IR spectroscopy. In all cases ammonia is first coordinated over Lewis acid sites and later undergoes hydrogen abstraction giving rise either to NH2 amide species or to its dimeric form N2H4, hydrazine. Other species, tentatively identified as imide NH, nitroxyl HNO, nitrogen anions N2− and azide anions N3− are further observed over CuO/TiO2. The comparison of the infrared spectra of the species arising from both NH3 and N2H4 adsorbed over CuO/TiO2 strongly suggest that N2H4 is an intermediate in NH3 oxidation over this active selective catalytic reduction (SCR) and selective catalytic oxidation (SCO) catalysts. This implies that ammonia is activated in the form of NH2 species for both SCR and SCO, and it can later dimerize. Ammonia protonation to ammonium ion is detected over V2O5-based systems, but not over CuO/TiO2, in spite of the high SCR and SCO activity of this catalyst. Consequently Brönsted acidity is not necessary for the SCR activity. 相似文献
5.
Catalytic performance of Sn/Al2O3 catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NOx by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO2 had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al2O3 (SG) catalyst, and the maximum NO2 conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NOx desorption accompanied with O2 around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H2O and SO2 at low temperature, and the temperature window was also broadened in the presence of H2O and SO2, however the NOx desorption and NO conversion decreased sharply on the 300 ppm SO2 treated catalyst, the catalytic activity was inhibited by the presence of SO2 due to formation of sulfate species (SO42−) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al2O3 (SG) was not decreased in the presence of large oxygen. 相似文献
6.
Antonio de Lucas-Consuegra Fernando Dorado Carmen Jimnez-Borja Jos L. Valverde 《Applied catalysis. B, Environmental》2008,78(3-4):222-231
In this work, we have investigated for the first time the selective catalytic reduction of N2O by C3H6 over an electrochemical catalyst (Pt/K-βAl2O3). It was evaluated the influence of the reaction conditions (temperature, oxygen concentration, water vapour presence and time on stream treatment under reaction conditions) on the catalytic performance of the electrochemical catalyst. Electrochemical pumping of potassium ions to the Pt catalyst working electrode strongly increased the N2O reduction rate, activating the catalyst at lower temperatures. However, it was found that the efficiency of the electrochemical promotion decreased as the oxygen concentration increased because of a strong inhibition of propene adsorption and a relative increase of the oxygen coverage. On the contrary, the presence of potassium ions on the Pt catalyst strongly decreased the inhibiting effect of water vapour, increasing the catalytic activity of the catalyst. In addition, the catalyst stability was confirmed by a deactivation study. It was found that a long term treatment at high temperature under operating conditions had a positive effect on the efficiency of the Pt/K-βAl2O3 electrochemical catalyst. 相似文献
7.
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
8.
An In2O3/Al2O3 catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO2 in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NOX adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO2, and the amount of ad-NO3− species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO2 enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO2 at low temperature, because active C3H6 (partially oxidized C3H6) is crucial at low temperature. 相似文献
9.
The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al2O3 with a bulk oxide has been investigated. The oxides studied were: Co3O4, Mn2O3, Cr2O3, CuO, Fe2O3, NiO, CeO2, SnO2, ZnO and V2O5. Under lean C3H6-SCR conditions, these oxides (with the exception of SnO2) convert selectively NO to NO2. When mechanically mixed with Au/Al2O3, the Mn2O3 and Co3O4 oxides and, to a much greater extent, CeO2 act synergistically with this catalyst greatly enhancing its SCR performance. It was found that their synergistic action is not straightforwardly related to their activity for NO oxidation to NO2. The exhibited catalytic synergy may be due to the operation of either remote control or a bifunctional mechanism. In the later case, the key intermediate must be a short-lived compound and not the NO2 molecule in gas-phase. 相似文献
10.
Stefanie Tamm Louise Olsson Sebastian Fogel Pär Gabrielsson Magnus Skoglundh 《American Institute of Chemical Engineers》2013,59(11):4325-4333
A global kinetic model which describes H2‐assisted NH3‐SCR over an Ag/Al2O3 monolith catalyst has been developed. The intention is that the model can be applied for dosing NH3 and H2 to an Ag/Al2O3 catalyst in a real automotive application as well as contribute to an increased understanding of the reaction mechanism for NH3‐SCR. Therefore, the model needs to be simple and accurately predict the conversion of NOx. The reduction of NO is described by a global reaction, with a molar stoichiometry between NO, NH3 and H2 of 1:1:2. Further reactions included in the model are the oxidation of NH3 to N2 and NO, oxidation of H2, and the adsorption and desorption of NH3. The model was fitted to the results of an NH3‐TPD experiment, an NH3 oxidation experiment, and a series of H2‐assisted NH3‐SCR steady‐state experiments. The model predicts the conversion of NOx well even during transient experiments. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4325–4333, 2013 相似文献
11.
The selective catalytic reduction (SCR) of NOx (NO + NO2) by NH3 in O2 rich atmosphere has been studied on Cu-FAU catalysts with Cu nominal exchange degree from 25 to 195%. NO2 promotes the NO conversion at NO/NO2 = 1 and low Cu content. This is in agreement with next-nearest-neighbor (NNN) Cu ions as the most active sites and with NxOy adsorbed species formed between NO and NO2 as a key intermediate. Special attention was paid to the origin of N2O formation. CuO aggregates form 40–50% of N2O at ca. 550 K and become inactive for the SCR above 650 K. NNN Cu ions located within the sodalite cages are active for N2O formation above 600 K. This formation is greatly enhanced when NO2 is present in the feed, and originated from the interaction between NO (or NO2) and NH3. The introduction of selected co-cations, e.g. Ba, reduces very significantly this N2O formation. 相似文献
12.
The objective of this work was to study the promotional effect of Pt on Co-zeolite (viz. mordenite, ferrierite, ZSM-5 and Y-zeolite) and Co/Al2O3 on the selective catalytic reduction (SCR) of NOx with CH4 under dry and wet reaction stream. After being reduced in H2 at 350°C, the PtCo bimetallic zeolites showed higher NO to N2 conversion and selectivity than the monometallic samples, as well as a combination of the latter samples such as mechanical mixtures or two-stage catalysts. After the same pretreatment, under wet reaction stream, the bimetallic samples were also more active. Among the other catalysts studied with 5% of water in the feed, (NO = CH4 = 1000 ppm, O2 = 2%), the NO conversion dropped to zero over Co2.0Mor at 500°C and GHSV = 30,000 h−1, whereas it is 20% in Pt0.5Co2.0Mor. In Pt/Co/Al2O3 the NOx conversion dropped below 5% with only 2% of water under the same reaction conditions. The specific activity given as molecules of NO converted per total metal atom per second were 16.5 × 10−4 s−1 for Pt0.5Co2.0Fer, 13 × 10−4 s−1 for Pt0.5Co2.0Mor, 4.33 × 10−4 s−1 for Pt0.5Co2.0ZSM-5 and 0.5 × 10−4 s−1 for Pt/Co/Al2O3. The Y-zeolite-based samples were inactive in both mono and bimetallic samples. The species initially present in the solid were Pt° and Co°, together with Co2+ and Pt2+ at exchange positions. Co° seems not to participate as an active site in the SCR of NOx. Those species remained after the reaction but some reorganization occurred. A synergetic effect among the different species that enhances both the NO to NO2 reaction, the activation of CH4 and also the ability of the catalyst to adsorb NO, could be responsible for the high activity and selectivity of the bimetallic zeolites. 相似文献
13.
C.M.L. Scholz V.R. Gangwal M.H.J.M. de Croon J.C. Schouten 《Applied catalysis. B, Environmental》2007,71(3-4):143-150
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
14.
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
15.
Performance of NOx 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 NOx trap, Pt–Ba/Al2O3. These were done at 950 °C for 3 h, in air and in 1% H2/N2, respectively. Lean aging had a severe impact on NOx trap performance, including HC and CO oxidation, and NH3 and N2O 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 NOx trap and two model NOx traps, Pt–Ba/Al2O3 and Pt–Ba–Ce/Al2O3. Pretreatments were done at 600 °C for 10 min, and used feed gas that simulated diesel exhaust under several conditions. Lean pretreatment severely suppressed NOx, HC, CO, NH3 and N2O activities for the ceria-containing NOx traps, but had no impact on Pt–Ba/Al2O3. 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 NOx traps for light-duty diesel vehicles. 相似文献
16.
The selective catalytic reduction (SCR) of NO by hydrocarbon is an efficient way to remove NO emission from lean-burn gasoline and diesel exhaust. In this paper, a thermally and hydrothermally stable Al–Ce-pillared clay (Al–Ce-PILC) was synthesized and then modified by SO42−, whose surface area and average pore diameter calcined at 773 K were 161 m2/g and 12.15 nm, respectively. Copper-impregnated Al–Ce-pillared clay catalyst (Cu/SO42−/Al–Ce-PILC) was applied for the SCR of NO by C3H6 in the presence of oxygen. The catalyst 2 wt% Cu/SO42−/Al–Ce-PILC showed good performance over a broad range of temperature, its maximum conversion of NO was 56% at 623 K and remained as high as 22% at 973 K. Furthermore, the presence of 10% water slightly decreased its activity, and this effect was reversible following the removal of water from the feed. Py-IR results showed SO42− modification greatly enhanced the number and strength of Brönsted acidity on the surface of Cu/SO42−/Al–Ce-PILC, which played a vital role in the improvement of NO conversion. TPR and XPS results indicated that both Cu+ and isolated Cu2+ species existed on the optimal catalyst, mainly Cu+, as Cu content increased to 5 wt%, another species CuO aggregates which facilitated the combustion of C3H6 were formed. 相似文献
17.
Hiroto Imai Toshiyuki Ogawa Kazuo Sugimoto Masakazu Kataoka Yumo Tanaka Takehiko Ono 《Applied catalysis. B, Environmental》2005,55(4):259-265
The Co/MFI(SiO2/Al2O3 = 30) were prepared by a precipitation method with NaOCl in alkali solutions exhibited high activities to N2 at 250 °C for the selective catalytic reduction (SCR) of NOx. These catalysts showed two UV–vis bands at 700 and 400 nm, indicating the presence of octahedral Co(III) as well as tetrahedral Co(II). The high SCR activity over such Co(III, II)/MFI(30) seems to come from Co(III)---O moieties. The Co(II)MFI(30) catalysts prepared from Co(II)Cl2 exhibited low SCR activities due to the presence of tetrahedral Co(II) ions in MFI. Less CO formation occurred over Co/MFI catalysts. The Fe/MFI(30) catalyst exhibited high activity due to the presence of some Fe---O species in MFI but more amount of CO were produced during SCR. H/MFI(30) catalyst exhibited a good SCR activity. However, more amount of carbonaceous deposits were produced on it. The correlation between acid concentration and SCR activity was discussed over H/MFIs. 相似文献
18.
R. W. van den Brink S. Booneveld M. J. F. M. Verhaak F. A. de Bruijn 《Catalysis Today》2002,75(1-4):227-232
The nitric acid industry is a source of both NOx and N2O. The simultaneous selective catalytic reduction of both compounds using propane as a reductant has been investigated. A stacked catalyst bed with first a Co-ZSM-5 catalyst and second a Pd/Fe-ZSM-5 catalyst gives >80% conversion of N2O and NOx above 300 °C at atmospheric pressure. At 4 bar absolute pressure (bara) the Co-ZSM-5 DeNOx catalyst shows higher NOx and propane conversion. This leaves not enough propane for the Pd/Fe-ZSM-5 DeN2O catalyst, which causes a ‘dip’ in N2O conversion. Reducing the space velocity (SV) of the first catalyst bed secures high NOx and N2O conversions from 300 °C and up at 4 bara. 相似文献
19.
Irene Malpartida Maria Angeles Larrubia Vargas Luis J. Alemany Elisabetta Finocchio Guido Busca 《Applied catalysis. B, Environmental》2008,80(3-4):214-225
Pt–Ba–Al2O3 active and selective for NOx storage and selective reduction to N2 has been prepared and tested. Characterization of the parent Al2O3, Pt–Al2O3 and Ba–Al2O3 materials, as well as of Pt–Ba–Al2O3 catalyst in the oxidized, reduced and sulphated state has been performed by FT-IR spectroscopy of low-temperature adsorbed carbon monoxide and of adsorbed acetonitrile. XRD, TEM and XPS analyses have also been performed. Evidence for the predominance of Ba species, which are highly dispersed on the alumina support surface, and may be carbonated or sulphated, has been provided. Competitive interaction of Pt and Ba species with the surface sites of alumina has also been found. 相似文献
20.
Todd J. Toops D. Barton Smith William P. Partridge 《Applied catalysis. B, Environmental》2005,58(3-4):245-254
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