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1.
Deactivation of catalysts based on either manganese oxides, copper oxides, platinum, palladium or combinations of these metal oxides and noble metals supported on γ-alumina was studied. The activity of the catalysts for the oxidation of carbon monoxide, naphthalene and methane, in a mixture resembling the flue gases from wood combustion, was measured before and after exposure of the catalysts either to a temperature of 900°C in the presence of steam or to sulphur dioxide. Most of the mixed catalysts were more resistant to hydrothermal and sulphur treatments than the catalysts with a single active component. After the hydrothermal treatment the activity of the MnO x catalyst was enhanced. When Pt is combined with MnO x or CuO x, the loss of activity of Pt was decreased during the hydrothermal treatment. Also, the hydrotreated mixed MnO x–Pd and CuO x–Pd catalysts were more active than the treated Pd catalyst for the oxidation of methane. After sulphur treatment, the activities of the mixed MnO x–Pt (Pt: 0.05 mol%), MnO x–Pd and CuO x–Pd catalysts were improved for the oxidation of carbon monoxide and naphthalene. Among the catalysts studied, the MnO x–Pt, CuO x–Pt and CuO x–Pd catalysts, with a metal oxide and a noble metal loading of 10 and 0.1 mol%/γ-alumina, respectively, had the best combination of activity, thermal stability and resistance to sulphur treatment. 相似文献
2.
MnO x–CeO 2 mixed oxides with a Mn/(Mn + Ce) molar ratios of 0–1 were prepared by a modified coprecipitation method and investigated for the complete oxidation of formaldehyde. The MnO x–CeO 2 with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnO x–CeO 2 mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnO x–CeO 2 solid solution greatly improved the low-temperature reducibility, resulting in a higher catalytic activity for the oxidation of formaldehyde. Promoting effect of Pt on the MnO x–CeO 2 mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnO x–CeO 2 catalyst prepared from chlorine-free precursor showed extremely high activity and stability after pretreatment with hydrogen at 473 K. 100% conversion of formaldehyde was achieved at ambient temperature and no deactivation was observed for 120 h time-on-stream. The promoting effect of Pt was ascribed to enhance the effective activation of oxygen molecule on the MnO x–CeO 2 support. 相似文献
3.
The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O 2. Among the Ba catalysts supported on single-component metal oxides, Ba/Co 3O 4 and Ba/CeO 2 showed high NO decomposition activities, while Ba/Al 2O 3, Ba/SiO 2, and Ba/TiO 2 exhibited quite low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found that the activities were significantly enhanced using Ce–Mn mixed oxides as support materials. XRD results indicated the formation of CeO 2–MnO x solid solutions with the cubic fluorite structure. O 2-TPD of the CeO 2–MnO x solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO 2–MnO x solid solutions were larger than those of pure CeO 2 and Mn 2O 3. These effects caused by the addition of Mn are responsible for the enhanced activities of the Ba catalysts supported on Ce–Mn mixed oxides. 相似文献
4.
MnO x–CeO 2 mixed oxides prepared by sol–gel method, coprecipitation method and modified coprecipitation method were investigated for the complete oxidation of formaldehyde. Structure analysis by H 2-TPR and XPS revealed that there were more Mn 4+ species and richer lattice oxygen on the surface of the catalyst prepared by the modified coprecipitation method than those of the catalysts prepared by sol–gel and coprecipitation methods, resulting in much higher catalytic activity toward complete oxidation of formaldehyde. The effect of calcination temperature on the structural features and catalytic behavior of the MnO x–CeO 2 mixed oxides prepared by the modified coprecipitation was further examined, and the catalyst calcined at 773 K showed 100% formaldehyde conversion at a temperature as low as 373 K. For the samples calcined below 773 K, no any diffraction peak corresponding to manganese oxides could be detected by XRD measurement due to the formation of MnO x–CeO 2 solid solution. While the diffraction peaks corresponding to MnO 2 phase in the samples calcined above 773 K were clearly observed, indicating the occurrence of phase segregation between MnO 2 and CeO 2. Accordingly, it was supposed that the strong interaction between MnO x and CeO 2, which depends on the preparation route and the calcination temperature, played a crucial role in determining the catalytic activity toward the complete oxidation of formaldehyde. 相似文献
5.
Kinetic study of CO oxidation in combination with experiments of temperature-programmed oxidation (TPO) and reduction (TPR) have been performed on various unsupported crystalline manganese oxides (MnO x); while the reactivity shows an order of MnO ≤ MnO 2 < Mn 2O 3 in a mixture of unit ratio of O 2/CO at/below 523 K. We propose that under the current conditions the interaction of adsorbed CO and O is mainly responsible for CO 2 formation on Mn 2O 3 and MnO 2 catalysts, following either the Langmuir–Hinshelwood mechanism or Eley–Rideal mechanism. Meanwhile, direct evidence from transient CO oxidation suggests that the Mars-van-Krevelen mechanism may occur for all catalysts simultaneously, especially, it is predominant for the MnO catalyst. The evidence of structural modifications during reaction was confirmed by Raman spectra obtained from used MnO. 相似文献
6.
Combustion of CO, ethyl acetate and ethanol was studied over CuO x/Al 2O 3, CuO x–CeO 2/Al 2O 3, CuMn 2O 4/Al 2O 3 and Mn 2O 3/Al 2O 3 catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuO x loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuO x–CeO 2/Al 2O 3 catalyst is more active than the CuMn 2O 4/Al 2O 3 catalyst for the oxidation of CO but the CuMn 2O 4/Al 2O 3 catalyst is more active for the combustion of ethyl acetate and ethanol. Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuOx–CeO2/Al2O3 and CuMn2O4/Al2O3 catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed. Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn2O4 and Mn2O3, respectively, on Al2O3. 相似文献
7.
The reaction between hydrogen and NO was studied over 1 wt.% Pd supported on NO x-sorbing material, MnO x–CeO 2, at low temperatures. The result of pulse mode reactions suggest that NO x adsorbed as nitrate and/or nitrite on MnO x–CeO 2 was reduced by hydrogen, which was spilt-over from Pd catalyst. The NO x storage and reduction (NSR) cycles were carried out over Pd/MnO x–CeO 2 in a conventional flow reactor at 150 °C. In a storage step, NO was removed by the oxidative adsorption from a stream of 0.04–0.08% NO, 5–10% O 2, and He balance. This was followed by a reducing step, where a stream of 1% H 2/He was supplied to ensure the conversion of nitrate/nitrite to N 2 and thus restore the adsorbability. It was revealed that the NSR cycle is much more suitable for the H 2–deNO x process in excess O 2, compared to a conventional steady state reaction mode. 相似文献
8.
The catalytic activity of a series of CeO 2–ZrO 2 mixed oxides in the total oxidation of methane and light hydrocarbons has been investigated. The influence of dopants like Mn and Cu has also been studied. It is shown that both MnO x and CuO at low loading dissolve within the ceria–zirconia lattice. This strongly influences the redox behaviour of the catalysts by promoting low-temperature reduction of Ce 4+. In addition, the ternary oxides show better stability to repeated redox cycles, which is attributed to the presence of ZrO 2. The catalytic activity of pure CeO 2 is also enhanced in the presence of ZrO 2, reaching a maximum with Ce 0.92Zr 0.08O 2; a further promotion of activity is observed with the introduction of MnO x and CuO dissolved into CeO 2–ZrO 2 lattice. 相似文献
9.
The selective catalytic reduction of NO x 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–CH 4–O 2 reaction, Ru, Rh, Pd, Ir, and Pt showed promotion effect on NO x reduction, while for the NO 2–CH 4–O 2 reaction, only Rh and Pd showed promotion effect. Over intact and Rh, Pd, Ag, and Au-loaded sulfated zirconia, NO x conversion in NO 2–CH 4–O 2 reaction was significantly higher than that in NO–CH 4–O 2 reaction, while clear difference was not observed over Ru, Ir, and Pt-loaded sulfated zirconia. Comparison of [NO 2]/([NO]+[NO 2]) in the effluent gases in NO–O 2 and NO 2–O 2 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 NO x reduction by methane can be categorized into the following three groups: (i) low activity for NO oxidation to NO 2, and high activity for NO 2 reduction to N 2 (Pd, Rh); (ii) high activity for NO oxidation to NO 2, and low activity for NO 2 reduction to N 2 (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 NO x by methane. 相似文献
10.
Ce 0.5Zr 0.5O 2, Ce 0.5Zr 0.2Mn 0.3O 2 and Ce 0.5Mn 0.5O 2 were prepared by citric acid sol–gel method. The effect of manganese on the structural and redox properties of ceria-based mixed oxides was investigated by means of powder X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller analyses, temperature-programmed reduction and catalytic activity evaluation in the presence of excess O 2. The results showed that some Mn cations could enter into the ceria lattice to form solid solutions. Mn 3O 4 appeared due to the instability of the mixed oxides with increment of the Mn doping ratio while another oxide Mn 2O 3 is detected in the physical mixture of ceria and manganese oxide. These Mn-doped mixed oxides, especially Ce 0.5Mn 0.5O 2, presented better catalytic activities than Ce 0.5Zr 0.5O 2 and even Pt-loaded catalyst for total oxidation of C 3H 8 and oxidative sorption of NO in the presence of excess oxygen. The oxidation ability of Mn and the strong interaction between Mn and Ce were suggested to promote the oxygen storage/transport capacity of the mixed oxides as well as reactive adsorption of nitric oxide and hydrocarbons. 相似文献
11.
This work aims at exploring the thermal ageing mechanism of Pt on ceria-based mixed oxides and the corresponding effect on the oxygen storage capacity (OSC) performance of the support material. Pt was supported on low-surface-area CeO 2–ZrO 2–La 2O 3 mixed oxides (CK) by impregnation method and subsequently calcined in static air at 500, 700 and 900 °C, respectively. The evolutions of textural, microstructural and redox properties of catalysts after the thermal treatments were identified by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and high-resolution transmission electron microscope (HRTEM). The results reveal that, besides the sintering of Pt, encapsulation of metal by the mixed oxides occurs at the calcination temperature of 700 °C and above. The burial of Pt crystallites by support particles is proposed as a potential mechanism for the encapsulation. Further, the HRTEM images show that the distortion of the mixed oxides lattice and other crystal defects are distributed at the metal/oxides interface, probably indicating the interdiffusion/interaction between the metal and mixed oxide. In this way, encapsulation of Pt is capable to promote the formation of Ce 3+ or oxygen vacancy on the surface and in the bulk of support. The OSC results show that the reducibility and oxygen release behavior of catalysts are related to both the metal dispersion and metal/oxides interface, and the latter seems to be more crucial for those supported on low-surface-area mixed oxides. Judging by the dynamic oxygen storage capacity (DOSC), oxygen storage capacity complete (OSCC) and oxygen releasing rate, the catalyst calcined at 700 °C shows the best OSC performance. This evident promotion of OSC performance is believed to benefit from the partial encapsulation of Pt species, which leads to the increment of Ce 3+ or oxygen vacancies both on the surface and in the bulk of oxides despite a loss of chemisorption sites on the surface of metal particles. 相似文献
12.
Four series of cobalt-based catalysts, such as bare Co 3O 4 and CoO, CoO x–CeO 2 mixed oxides, CoO x supported over alumina and alumina–baria and CoMgAl and CoNiAl hydrotalcites have been synthesized and investigated for the oxidative degradation of phenol in the presence of ozone. Characterizations were obtained by several techniques in order to investigate the nature of cobalt species and their morphological properties, depending on the system. Analyses by XRD, BET, TPR, UV–visible diffuse reflectance spectroscopy and TG/DT were performed. The CoNiAl hydrotalcite exhibits, after 4 h of reaction, the highest phenol ozonation activity followed by Co(3 wt%)/Al2O3–BaO and CoMgAl. The samples Co(1 wt%)/Al2O3–BaO and Co(1 and 3 wt%)/Al2O3 show a comparable medium activity, while the oxidation properties of bare oxides Co3O4, CoO and CoOx–CeO2 are really low. Leaching of cobalt ions in the water solution was detected during the reaction, the amount varied depending on the nature of catalysts. A massive release was observed for the CoMgAl and CoNiAl hydrotalcites, while cobalt catalysts over alumina and alumina–baria look much more stable. The recycle of CoOx/Al2O3 and CoOx/Al2O3–BaO was studied by performing three consecutive cycles in the phenol oxidation. Because of the potential interest of the cobalt-supported catalysts in the ozonation process, the oxidative degradation of naphtol blue black was also investigated. On the basis of TPR and UV–visible results it appears that highly dispersed Co2+ ions especially present over Co(3 wt%)/Al2O3–BaO are the main active sites for phenol and naphtol blue black oxidative degradation by ozone. 相似文献
13.
The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO 2 (70, 85 wt.%)–Al 2O 3 (15, 0 wt.%)–WO x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N 2 physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO 3 bulk phase. The catalysts increased their SBET for about 15% promoted by Al 2O 3 addition. Various oxidation states of WO x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W 6+ and reduced-state WO x species (either W 4+ or W 0). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers. 相似文献
14.
Oxidation of a mixture of thiophene, benzothiophene and dibenzothiophene with hydrogen peroxide using supported Pd, Cr 2O 3, unsupported manganese oxides and a commercial Co-Mo/Al 2O 3 as catalysts has been studied in a mixture of hexadecane and acetonitrile. Based solely on the conversion of each organic sulfur compound, the ranking of catalyst efficiency found was: supported Pd > Cr 2O 3 ≈ manganese oxides ≈ Co-Mo/Al 2O 3. The influence of the calcination temperature on synthesized manganese oxides was also investigated. Mn 3O 4, amorphous manganese compounds, Mn 2O 3 and MnO 2 showed a similar catalytic activity independent of the hydrogen peroxide concentration. According to these preliminary results, it seemed that the catalyzed decomposition of the hydrogen peroxide competes with the oxidative desulfurization, however, at short reaction time (10 min) conversions at around 60–70% of thiophene were reached. 相似文献
15.
High surface area CeO 2–ZrO 2 mixed oxides were treated at 900–950°C either under wet air or under successive reducing and oxidizing atmospheres in order to study the evolution of the oxygen storage capacity (OSC) of these solids after different aging treatments. Several complementary methods were used to characterize the redox behavior: temperature programmed reduction (TPR) by H 2, TPO, magnetic susceptibility measurements to obtain the Ce 3+ content, FT-IR spectroscopy of adsorbed methanol and a method to compare the oxygen buffering capacity (OBC) of the oxides. All the results confirm that the mixed oxides exhibit better redox properties than pure ceria, particularly after aging. The enhancement in the OSC at moderate temperature has to be related to a deeper penetration of the reduction process from the surface into the under-layers. Redox cycling aging promotes the reduction at low temperature of all the mixed oxides, the improvement being much more important for low surface area aged samples. The magnitude of this effect does not depend on the BET surface areas which have similar values after cycling. This underlines the critical influence that the preparation and activation procedure have on the final OSC behaviors of the ceria–zirconia mixed oxides. 相似文献
16.
Palladium catalysts supported on mixed oxides (Pd/Al 2O 3–MO x; M=Co, Cr, Cu, Fe, Mn, and Ni) were investigated for the low-temperature catalytic combustion of methane. Although the surface area decreased with increasing NiO in Pd/ mAl 2O 3– nNiO, Pd/Al 2O 3–36NiO demonstrated an excellent activity due to the small particle size of palladium. Also, the catalytic activity strongly depended on the composition of the support. Temperature-programmed desorption of oxygen revealed that the catalytic activity in the low-temperature region depends on the adsorption state of oxygen on palladium. The activity was enhanced when the amount of adsorbed oxygen increased. In-situ XRD analysis indicated that the PdO phase was thermally stabilized on Pd/Al 2O 3–36NiO. 相似文献
17.
Reaction mechanism of the reduction of nitrogen monoxide by methane in an oxygen excess atmosphere (NO–CH 4–O 2 reaction) catalyzed by Pd/H-ZSM-5 has been studied at 623–703 K in the absence of water vapor, in comparison with the mechanism for Co-ZSM-5. Kinetic isotope effect for the N 2 formation in NO–CH 4–O 2 vs. NO–CD 4–O 2 reactions was 1.65 at 673 K and decreased with a decrease in the reaction temperature. In addition, H–D isotopic exchange took place significantly in NO–(CH 4+CD 4)–O 2 reaction. These results are in marked contrast with the case of Co-ZSM-5, for which the C–H dissociation of methane is the only rate-determining step, and show that the C–H dissociation is slow but not the only rate-determining step in the case of Pd/H-ZSM-5. A reaction scheme was proposed, in which the relative rates of the three steps ((i)–(iii) below) vary depending on the reaction conditions. Further, in contrast to Co-ZSM-5, NO x–CH 4–O 2 reaction was much slower than CH 4–O 2 reaction for Pd/H-ZSM-5; the presence of NO x retards the reaction of CH 4 over the latter catalyst, while it accelerates the reaction over the former. It is suggested that CH 4 is activated directly by the Pd atoms in the case of Pd/H-ZSM-5, but by NO 2 strongly adsorbed on Co ion for Co-ZSM-5. The reaction order of the NO–CH 4–O 2 reaction with respect to NO pressure was consistent with this mechanism; 1.05 for Pd/H-ZSM-5 and 0.11 for Co-ZSM-5. 相似文献
18.
MnO x catalysts supported on alumina, titania or yttria-stabilised zirconia were studied in ethanol oxidation. Catalysts were characterized by determining their XRD, TPR, TPD-O 2 and TPD-NH 3 properties and light-off behavior. The effect of kind of carrier on activity in the ethanol oxidation and on selectivity to acetaldehyde (ACA) was determined. Relation between the TPR properties of the catalysts and their activity in ethanol conversion is suggested. The maximum of selectivity to ACA appears in the same sequence of temperatures as the first peak of oxygen desorption from supported MnO x catalysts. 相似文献
19.
A study of CO oxidation by O 2 over Pt catalysts, promoted by MnO x and CoO x, is described. The activities of Pt/SiO 2, Pt/MnO x/SiO 2 and Pt/CoO x/SiO 2 are compared with commercial Pt/Al 2O 3, Pt/Rh/Al 2O 3 and Pt/CeO x/Al 2O 3 catalysts. Since these catalysts differ in dispersion and weight loading of platinum, the turnover frequencies are also compared. The following order in activity in CO oxidation after a reductive pretreatment is found: Pt/CoO x/SiO 2 > Pt/MnO x/SiO 2, Pt/CeO x/Al 2O 3 > Pt/Al 2O 3, Pt/Rh/Al 2O 3, Pt/SiO 2. Over Pt/CoO x/SiO 2 CO is already oxidised at room temperature. Possible models to account for the high activity of Pt/CoO x/SiO 2 in the CO/O 2 reaction are presented and discussed. Partially reduced metal oxides are necessary to increase the activity of the Pt/CoO x/SiO 2, Pt/MnO x/SiO 2 or Pt/CeO x/Al 2O 3 catalysts. It was shown that mild ageing treatments did not affect the activity of the Pt/CoO x/SiO 2 catalyst in CO oxidation. 相似文献
20.
A series of V 2O 5–TiO 2 aerogel catalysts were prepared by sol–gel method with subsequent supercritical drying with CO 2. The aerogel catalysts showed much higher surface areas and total pore volumes than V 2O 5–TiO 2 xerogel and impregnated V 2O 5–TiO 2 catalysts. Two species of surface vanadium in the aerogel catalysts were identified by Raman measurements: monomeric vanadyl and polymeric vanadates. The selective oxidation of hydrogen sulfide in the presence of excess water and ammonia was studied over these catalysts. Aerogel catalysts showed very high conversion of H 2S without harmful emission of SO 2. Temperature programmed reduction (TPR), XRD and Raman analyses revealed that the high catalytic performance of the aerogel catalysts originated from their highly dispersed VO x species and high reducibility. 相似文献
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