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1.
The effectiveness of Ag/Al2O3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al2O3, and Al(OH)3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O2, NO + O2-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C3H6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C3H6 conversion was achieved over Ag/Al2O3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al2O3 (I) is deemed to be crucial for NO selective reduction into N2. By contrast, a high C3H6 conversion simultaneously with a moderate N2 yield was observed over Ag/Al2O3 (II) prepared from a γ-Al2O3 source. The larger particles of AgmO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al2O3 (III) was obtained via employing a Al(OH)3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al2O3 (I). A subsequent calcination of Ag/Al2O3 (III) at 800 °C led to the generation of Ag/Al2O3 (IV) catalyst yielding a significant enhancement in both N2 yield and C3H6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al2O3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al2O3 (II and V) > Ag/Al2O3 (IV) > Ag/Al2O3 (I) > Ag/Al2O3 (III) and Al2O3 (I). The formation of nitrate species is an important step for the deNOx process, which can be promoted by increasing O2 feed concentration as evidenced by NO + O2-TPD study for Ag/Al2O3 (I), achieving a better catalytic performance.  相似文献   

2.
Reaction activities of several developed catalysts for NO oxidation and NOx (NO + NO2) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co3O4 based catalysts are the most active ones for both NO oxidation and NOx reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co3O4 catalyst, the effects of calcination temperatures, SO2 concentration, optimum SV for 50% conversion of NO to NO2 were determined. Also, Co3O4 based catalysts (Co3O4-WO3) exhibit significantly higher conversion than all the developed DeNOx catalysts (supported/unsupported) having maximum conversion of NOx even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N2O formation over Co3O4-WO3 catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N2O over all the catalysts. The effect of SO2 concentration on NOx reduction is found to be almost negligible may be due to the presence of WO3 that resists SO2 oxidation.  相似文献   

3.
Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO2 and Al2O3 on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO2 catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al2O3 catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al2O3 catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O2/CO ratio due to the oxidation of H2 which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO2 showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O2/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al2O3, CuO/CeO2), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX.  相似文献   

4.
The catalytic activity of Pt on alumina catalysts, with and without MnOx incorporated to the catalyst formulation, for CO oxidation in H2-free as well as in H2-rich stream (PROX) has been studied in the temperature range of 25–250 °C. The effect of catalyst preparation (by successive impregnation or by co-impregnation of Mn and Pt) and Mn content in the catalyst performance has been studied. A low Mn content (2 wt.%) has been found not to improve the catalyst activity compared to the base catalyst. However, catalysts prepared by successive impregnation with 8 and 15 wt.% Mn have shown a lower operation temperature for maximum CO conversion than the base catalyst with an enhanced catalyst activity at low temperatures with respect to Pt/Al2O3. A maximum CO conversion of 89.8%, with selectivity of 44.9% and CO yield of 40.3% could be reached over a catalyst with 15 wt.% Mn operating at 139 °C and λ = 2. The effect of the presence of 5 vol.% CO2 and 5 vol.% H2O in the feedstream on catalysts performance has also been studied and discussed. The presence of CO2 in the feedstream enhances the catalytic performance of all the studied catalysts at high temperature, whereas the presence of steam inhibits catalysts with higher MnOx content.  相似文献   

5.
Mn/MFI catalysts were prepared by different methods and probed as catalysts for the catalytic reduction of NOx with CH4 or iso-butane in a gas flow containing excess O2. Mn/MFI with high manganese loading was obtained by solid state ion exchange (SSI). The intensity of an IR band at 957 cm−1, which is due to the perturbation of zeolite lattice vibrations by Mn ions attached to cage walls is proportional to the Mn content of the catalysts. Conversely, the intensity of the 3610 cm−1 band, assigned to Brønsted acid sites decreases linearly with the Mn loading. A catalyst obtained by exchanging Na/MFI with an aqueous solution of Mn acetate is found most active for NOx reduction with methane. Transport by surface diffusion of Mn ions from MnI2 to exchange positions in MFI is more efficient than their transport through the gas phase. High NO conversion over proton-free catalysts indicates that protons are not instrumental in NOx reduction over Mn/MFI.  相似文献   

6.
Selective catalytic reduction (SCR) of NO with methane in the presence of excess oxygen has been investigated over a series of Mn-loaded sulfated zirconia (SZ) catalysts. It was found that the Mn/SZ with a metal loading of 2–3 wt.% exhibited high activity for the NO reduction, and the maximum NO conversion over the Mn/SZ catalyst was higher than that over Mn/HZSM-5. NH3–TPD results of the catalysts showed that the sulfation process of the supports resulted in the generation of strong acid sites, which is essential for the SCR of NO with methane. On the other hand, the N2 adsorption and the H2–TPR of the catalysts demonstrated that the presence of the SO42− species promoted the dispersion of the metal species and made the Mn species less reducible. Such an increased dispersion of metal species suppressed the combustion reaction of CH4 by O2 and increased the selectivity towards NO. The Mn/SZ catalysts prepared by different methods exhibited similar activities in the SCR of NO with methane, indicating the importance of SO42−. The most attractive feature of the Mn/SZ catalysts was that they were more tolerant to water and SO2 poisoning than Mn/HZSM-5 catalysts and exhibited higher reversibility after removal of SO2.  相似文献   

7.
Pt45Ru45M10/C (M = Fe, Co, and Ni) catalysts were synthesized and physical and electrochemical properties were analyzed by XRD, TEM, CO stripping and methanol electro-oxidation activity measurement. Among these catalysts, the Pt45Ru45Fe10/C catalyst exhibited the highest mass activity of 2.6 A/g catal. while those of the Pt45Ru45Co10/C and Pt45Ru45Ni10/C catalysts were 2.2 and 2.5 A/g catal., respectively. In the case of specific activity, the catalysts exhibited much higher activities of 110 (130%), 120 (140%) and 150 (170%) mA/m2 for the Fe, Co and Ni incorporated catalysts, respectively, than 88 mA/m2 of a commercial PtRu/C catalyst.  相似文献   

8.
A 5 wt% CoOx/TiO2 catalyst has been used to study the effect of calcination temperature on the activity of this catalyst for CO oxidation at 100 °C under a net oxidizing condition in a continuous flow type fixed-bed reactor system, and the catalyst samples have been characterized using TPD, XPS and XRD measurements. The catalyst after calcination at 450 °C gave highest activity for this low-temperature CO oxidation, and XPS measurements yielded that a 780.2-eV Co 2p3/2 main peak appeared with this catalyst sample and this binding energy was similar to that measured with pure Co3O4. After calcination at 570 °C, the catalyst, which had possessed practically no activity in the oxidation reaction, gave a Co 2p3/2 main structure peak at 781.3 eV which was very similar to those obtained for synthesized ConTiOn+2 compounds (CoTiO3 and Co2TiO4), and this catalyst sample had relatively negligible CO chemisorption as observed by TPD spectra. XRD peaks indicating only the formation of Co3O4 particles on titania surface were developed in the catalyst samples after calcination at temperatures ≥350 °C. Based on these characterization results, five types of Co species could be modeled to exist with the catalyst calcined at different temperatures. Among these surface Co species, the Type A clean Co3O4 particles were predominant on a sample of the catalyst after calcination at 450 °C and highly active for CO oxidation at 100 °C, and the calcination at 570 °C gave the Type B Co3O4 particles with complete ConTiOn+2 overlayers inactive for this oxidation reaction.  相似文献   

9.
The WO3–TiO2 catalysts with different WO3 loadings prepared by the coprecipitation method were investigated in comparison with those prepared by the conventional impregnation method for the activity and durability in the high temperature SCR of NO by NH3 and the structural and physico-chemical properties which were characterized by BET and XRD measurements, IR, Raman and XPS spectroscopies. The catalyst prepared by coprecipitation, as compared with that prepared by impregnation, was found to exhibit a higher SCR activity at high temperatures and also to possess a larger surface area, higher Brønsted acidity and larger monolayer capacity of the support with WO3. Increasing the WO3 loading of the catalysts enhances the SCR activity and simultaneously increases the Brønsted acidity. The observed improvement of SCR activity for the catalyst prepared by coprecipitation is mainly attributed to the higher Brønsted acidity and the presence of the more highly dispersed WO3 species which is suggested by the larger monolayer capacity of ca. 13 μmol(W)/m2 and no crystalline WO3 on TiO2 detected with XRD at the high WO3 loading up to 40 wt.%. The catalyst with 20 wt.% WO3, as compared with that prepared by impregnation, was found to exhibit a better thermal durability at high temperatures from 550 to 600 °C. The better durability is attributed to that the reduction of the surface area and the formation and subsequent growth of crystalline WO3 upon aging are more remarkably inhibited.  相似文献   

10.
CO and CH4 combined oxidation tests were performed over a Pd (70 g/ft3)/Co3O4 monolithic catalyst in conditions of GHSV = 100,000 h−1 and feed composition close to that of emission from bi-fuel vehicles. The effect of SO2 (5 ppm) on CO and CH4 oxidation activity under lean condition (λ = 2) was investigated. The presence of sulphur strongly deactivated the catalyst towards methane oxidation, while the poisoning effect was less drastic in the oxidation of CO. Saturation of the Pd/Co3O4 catalytic sites via chemisorbed SO3 and/or sulphates occurred upon exposure to SO2. A treatment of regeneration to remove sulphate species was attempted by performing a heating/cooling cycle up to 900 °C in oxidizing atmosphere. Decomposition of PdO and Co3O4 phases at high temperature, above 750 °C, was observed. Moreover, sintering of Pd0 and PdO particles along with of CoO crystallites takes place.  相似文献   

11.
A series of CoOx/Al2O3 catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C3H8. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co3O4 crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoOx/Al2O3 catalyst shows high activity in SCR of NO by C3H8 (100% conversion of NO at 723 K, GHSV: 10,000 h−1). The activity of the selective catalytic reduction of NO by C3H8 increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl2O4 crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co3O4 crystallites catalyze the combustion of C3H8 only.  相似文献   

12.
The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV–VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV–VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV–VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O2). The low activity for N2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can, therefore, be related to the presence of metallic silver, which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2.  相似文献   

13.
A series of CeO2 promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N2O). Addition of CeO2 to Co3O4 led to an improvement in the catalytic activity for N2O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N2O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O2, H2O or NO. Methods of XRD, FE-SEM, BET, XPS, H2-TPR and O2-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO2 could increase the surface area of Co3O4, and then improve the reduction of Co3+ to Co2+ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N2O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO2, are responsible for the enhancement of catalytic activity of Co3O4.  相似文献   

14.
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   

15.
Hong He  Changbin Zhang  Yunbo Yu 《Catalysis Today》2004,90(3-4):191-materials
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   

16.
A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NOx reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NOy groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N2O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N2O and NO2 occurs and confirms that the formation of NO2 species is an essential step for NO reduction by CH4.  相似文献   

17.
A series of calcium-modified alumina-supported cobalt catalysts were prepared with a two-step impregnation method, and the effect of calcium on the catalytic performances of the catalysts for the partial oxidation of methane to syngas (CO and H2) was investigated at 750 °C. Also, the catalysts were characterized by XRD, TEM, TPR and (in situ) Raman. At 6 wt.% of cobalt loading, the unmodified alumina-supported cobalt catalyst showed a very low activity and a rapid deactivation, while the calcium-modified catalyst presented a good performance for this process with the CH4 conversion of 88%, CO selectivity of 94% and undetectable carbon deposition during a long-time running. Characterization results showed that the calcium modification can effectively increase the dispersion and reducibility of Co3O4, decrease the Co metal particle size, and suppress the reoxidation of cobalt as well as the phase transformation to form CoAl2O4 spinel phases under the reaction conditions. These could be related to the excellent catalytic performances of Co/Ca/Al2O3 catalysts.  相似文献   

18.
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   

19.
To get the low temperature sulfur resistant V2O5/TiO2 catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V2O5/TiO2 catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V2O5/TiO2 catalysts showed high catalytic activity for NH3 selective catalytic reduction (NH3-SCR) of NOx carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V2O5/TiO2 > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V2O5/TiO2 for maximum NOx conversion, which also showed high resistance to SO2 in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V2O5/TiO2 and compared with commercial W(10%)V2O5/TiO2 catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V2O5/TiO2 catalyst with temperature was observed. SO2 deactivation experiments were carried out for Sb(2%)/V2O5/TiO2 and W(10%)/V2O5/TiO2 at a temperature of 230 °C for 90 h, resulted Sb(2%)/V2O5/TiO2 was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V2O5/TiO2 than Sb(2%)/V2O5/TiO2 catalyst.  相似文献   

20.
A new catalyst composed of nickel oxide and cerium oxide was studied with respect to its activity for NO reduction by CO under stoichiometric conditions in the absence as well as the presence of oxygen. Activity measurements of the NO/CO reaction were also conducted over NiO/γ-Al2O3, NiO/TiO2, and NiO/CeO2 catalysts for comparison purposes. The results showed that the conversion of NO and CO are dependent on the nature of supports, and the catalysts decreased in activity in the order of NiO/CeO2 > NiO/γ-Al2O3 > NiO/TiO2. Three kinds of CeO2 were prepared and used as support for NiO. They are the CeO2 prepared by (i) homogeneous precipitation (HP), (ii) precipitation (PC), and (iii) direct decomposition (DP) method. We found that the NiO/CeO2(HP) catalyst was the most active, and complete conversion of NO and CO occurred at 210 °C at a space velocity of 120,000 h−1. Based on the results of surface analysis, a reaction model for NO/CO interaction over NiO/CeO2 has been proposed: (i) CO reduces surface oxygen to create vacant sites; (ii) on the vacant sites, NO dissociates to produce N2; and (iii) the oxygen originated from NO dissociation is removed by CO.  相似文献   

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