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1.
The effect of the Pd addition method into the fresh Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts (OSC material = CexZr1−xO2 mixed oxides) was investigated in this study. The CO + NO and CO + NO + O2 model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al2O3) catalyst than for the fresh (Pd + OSC)/Al2O3 catalyst during the CO + NO + O2 reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al2O3) catalyst was higher than that of the (Pd + OSC)/Al2O3 catalyst.  相似文献   

2.
More than 0.22 mmol of isolated VO4 species of V2O5/Al2O3 exhibited the highest evolution of the partial oxidation products (alcohol and ketone) in the oxidation of cyclohexane and cyclopentane. The conversion of cyclohexane and the selectivity of the partial oxidation products were achieved to be 0.49% and 85% over 0.8 g of 3.5 wt.% V2O5/Al2O3, respectively, where the K/A ratio was 6.2. In addition, V2O5/Al2O3 can selectively oxidize various hydrocarbons in the liquid phase by the one-step oxygen atom insertion to CH bond. The order of priority was tertiary carbon > secondary carbon > primary carbon > benzene ring.  相似文献   

3.
Surface-phase ZrO2 on SiO2 (SZrOs) and surface-phase La2O3 on Al2O3 (SLaOs) were prepared with various loadings of ZrO2 and La2O3, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH4/CO2 reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al2O3 and Pt/SiO2 catalysts. CO2 or CH4 pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO2 to form a stable surface-phase oxide. The lanthana cannot be spread well on Al2O3, but it forms a stable amorphous oxide with Al2O3. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO2 and Pt/Al2O3 by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO2 and Pt/Al2O3 catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO2 adsorbed on the basic sites of SZrOs and SLaOs.  相似文献   


4.
The physico-chemical characteristics and the reactivity of sub-monolayer V2O5-WO3/TiO2 deNOx catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO2 surface. The presence of tungsten oxide stabilizes the surface VIV and modifies the redox properties of V2O5/TiO2 samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V2O5-WO3/TiO2 catalysts exhibits higher activity than the binary V2O5/TiO2 and WO3/TiO2 reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.  相似文献   

5.
The surface properties of a series of V2O5 catalysts supported on different oxides (Al2O3, H–Na/Y zeolite, MgO, SiO2, TiO2 and ZrO2) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH3 adsorption. In the case of the V2O5/SiO2 system TEM images evidenced the presence of V2O5 crystallites, whereas such segregated phase was not observed for the other samples. VOx species resulted widely spread on the surface of Al2O3, H–Na/Y zeolite, MgO and SiO2, whereas on TiO2 and ZrO2 they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V2O5/TiO2 and V2O5/ZrO2 catalysts.  相似文献   

6.
The reduction of NOx by hydrogen under lean burn conditions over Pt/Al2O3 is strongly poisoned by carbon monoxide. This is due to the strong adsorption and subsequent high coverage of CO, which significantly increases the temperature required to initiate the reaction. Even relatively small concentrations of CO dramatically reduce the maximum NOx conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al2O3. In this case, although pure H2 and pure CO are ineffective for NOx reduction under lean burn conditions, H2/CO mixtures are very effective. With a realistic (1:3) H2:CO ratio, typical of actual exhaust gas, Pd/Al2O3 is significantly more active than Pt/Al2O3, delivering 45% NOx conversion at 160 °C, compared to >15% for Pt/Al2O3 under identical conditions. The nature of the support is also critically important, with Pd/Al2O3 being much more active than Pd/SiO2. Possible mechanisms for the improved performance of Pd/Al2O3 in the presence of H2+CO are discussed.  相似文献   

7.
The effect of the nature of vanadium species on benzene total oxidation   总被引:4,自引:0,他引:4  
The nature of the vanadium species present on V2O5/Al2O3 catalysts was investigated by using solid state 51V NMR, diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD) and temperature programmed reduction (TPR). 51V NMR and DRS analyses indicated the presence of V5+ in tetrahedral symmetry at low vanadium loading. A surface polymeric vanadium species and/or the bulk crystalline V2O5 were mainly observed at high vanadium loading as also detected by XRD. The positions of the absorption edges determined through the UV–VIS spectra allowed distinguishing between various tetrahedral symmetries. After TPR, the average oxidation state of vanadium depended on the vanadium content. The nature of vanadium species was related to the catalyst behavior on the benzene oxidation reaction. The catalysts containing high vanadium content were more active suggesting that a high amount of V4+ is responsible for the higher activity.  相似文献   

8.
A series of Pd/Al2O3 catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H2PdCl4, Pd(NO3)2 and Pd(AcAc)2) and pre-treatments. The mean particle size of reduced samples was determined by H2 chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed.  相似文献   

9.
Two series of catalysts, V2O5/TiO2 and modified V2O5/TiO2, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V2O5/TiO2. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V2O5/TiO2 with MoO3, WO3, Nb2O5 or Ta2O5, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.  相似文献   

10.
Conversion of CCl2F2 in the presence (hydrogenolysis) and absence of hydrogen was investigated on Al2O3, AlF3 and Pd/Al2O3 xerogel and aerogel catalysts. CCl2F2 was found to form CClF3 and CCl3F on Al2O3 and AlF3 in the presence and absence of hydrogen as well as on the Pd/Al2O3 catalysts in the absence of hydrogen. Overall activity increased during the hydrogenolysis reactions at 230°C as a function of time which was paralleled by a significant increase in the yield of CClF3 formed through a Cl/F-exchange reaction. X-ray diffraction patterns of the spent catalyst recovered after 3 h of hydrogenolysis confirmed the presence of Pd(C) (Pd–carbon solid solution) and AlF3 phases on Pd/Al2O3 catalysts indicated that the carbon incorporation into the Pd lattice and the transformation of Al2O3 to AlF3 starts at the initial stage of the reaction. It was concluded that AlF3 is responsible for the Cl/F-exchange reactions. CH4, a complete hydrogenation product, is formed during hydrogenolysis. Another route for its formation is the reaction between hydrogen in the gas phase and the interstitial carbon.  相似文献   

11.
通过浸渍法制备了Al_2O_3负载的Pd和Pt催化剂,考察催化剂的甲烷、乙烷和丙烷催化燃烧活性,以及助剂Ba对催化性能的影响。对于Pd/Al_2O_3催化剂,加入Ba使活性物种PdO颗粒变大和还原温度升高,形成更稳定的PdO活性物种,是Pd-Ba/Al_2O_3催化剂活性提升的主要原因。对于Pt/Al_2O_3催化剂,加入Ba助剂使活性物种Pt0含量降低,PtO_x与Al_2O_3载体相互作用增强,使PtO_x物种更难被还原为Pt~0,导致Pt-Ba/Al_2O_3催化剂活性降低。Pd和Pt催化剂催化烷烃氧化反应活性规律一致:丙烷乙烷甲烷。Pd/Al_2O_3催化剂有利于C—H键活化,Pt/Al_2O_3催化剂有利于C—C键活化。Pt/Al_2O_3催化剂对C1-C3烷烃氧化活性的差别明显大于Pd/Al_2O_3催化剂。Pt/Al_2O_3催化剂对碳比例高的烷烃活性更高。  相似文献   

12.
Alumina–silica mixed oxide, synthesized by the sol–gel technique, was used as a support for dispersing and stabilizing the active vanadia phase. The catalysts were characterized employing 51V and 1H solid-state MAS NMR, diffuse reflectance FT-IR, BET surface area measurements. The partial oxidation activities of the catalysts were tested using methanol oxidation as a model reaction. 51V solid-state NMR studies on the calcined catalysts showed the peaks corresponding to the presence of both tetrahedral and distorted octahedral vanadia species at low vanadia loadings and with an increase in V2O5 content, the 51V chemical shifts corresponding to amorphous V2O5 like phases were observed. DRIFTS studies of the catalysts indicated the vibrations corresponding tetrahedral vanadia species at low and medium loadings and at high V2O5 contents the vibrations corresponding V=O bonds of V2O5 agglomerates were observed. The V/Al–Si catalysts exhibited high selectivity for the dehydration product dimethyl ether in the methanol partial oxidation studies showing the predominance of the acidic nature of the alumina–silica support over the redox properties of the active vanadia phase.  相似文献   

13.
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   

14.
采用等体积浸渍法和还原法结合制备了Pd/Al_2O_3催化剂,通过N_2吸附-脱附、SEM、TEM、X射线衍射、X射线光电子能谱和CO原位漫反射傅里叶变换红外光谱等表征手段对制备的样品微观结构进行了系统分析,考察了不同Pd负载量和测试条件下CO催化氧化性能。实验结果表明,水合肼还原法实现了Pd在Al_2O_3载体上的均匀分散,Pd颗粒的直径在9 nm左右,且为Pd单质;负载后的催化剂呈现明显的中孔结构特征,有利于气体分子的扩散。在0.2%~0.5%的低负载质量分数下,CO的催化性能随着Pd负载量的增加而增加,随着CO进口浓度和空速的升高而逐渐降低,在进口浓度为0.05%,空速为4 017 h~(-1)时,不同负载量的催化剂均能使CO完全催化;温度对催化剂的催化效果影响显著,从常温到50℃催化剂的性能变化显著;湿度增加对催化有一定的促进作用。Pd负载质量分数0.5%的催化剂稳定性测试表明,催化剂能够在100 h内保持92%以上的稳定转化率。  相似文献   

15.
The effect of the TiO2–Al2O3 mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous HDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO2 into the support, and particularly over rich- and pure-TiO2-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO2. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil HDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO2 content and large differences are observed between the catalysts supported on pure Al2O3 and pure TiO2. In contrast, in the case of the thiophene test, the pure Al2O3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al2O3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al2O3- and pure TiO2-based catalysts is relatively small and dependent on the H2 pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H2 partial pressure on the thiophene HDS, and on the effect of H2S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking.  相似文献   

16.
Alumina-, silica-, and titania-supported vanadium oxide systems with V2O5 loadings ranging from 3 to 12 wt.%, corresponding to 0.02–0.09 V/(Al,Si,Ti) atomic ratios, were prepared by atomic layer deposition (ALD) and compared with the corresponding impregnated catalysts. The surface acidic properties of the supports and catalysts were investigated using ammonia adsorption microcalorimetry to determine the number and strength of the surface acid sites. Deposition of V2O5 on alumina and titania supports gave rise to catalysts with lower amounts of acid sites than the respective supports, while for the samples prepared on silica, an increase of the number of acid sites was observed after V2O5 deposition. As a common trend, the surface acid strength was greater for the ALD catalysts than for the impregnated ones, suggesting a stronger interaction of the VO species with the support centers, which act as electron attractor centers creating Lewis-like vanadium species. Redox cycles were performed, involving temperature programmed reduction (TPR) analyses separated by an oxidation treatment (TPO). The results evidenced the good reversibility of the redox behavior of the vanadium centers in every case, while significant differences were observed when comparing the temperatures of reduction (Tmax). Lower Tmax values were observed for the better dispersed vanadia catalysts. After reduction, the V centers had a final formal average oxidation state corresponding to +3 or less (+2.5 to +2). The reactivity of the vanadia systems was examined by measuring their performance for the oxidation of o-xylene to phthalic anhydride. Activity tests indicated the superior selectivity of the V2O5 systems based on the more acidic supports (Al2O3 and TiO2). The nature of the support governed the activity, and the more concentrated catalysts gave rise to improved selectivity to phthalic anhydride.  相似文献   

17.
赵乐乐  王守信  王远洋 《工业催化》2015,23(11):874-881
以活性成分负载量、负载顺序和焙烧温度等关键制备参数因素进行正交实验设计制备了V_2O_5-WO_3/TiO_2催化剂,对其进行XRD和TPR表征,并在自行设计搭建的SCR烟气脱硝实验平台上评价其(300~390)℃的SCR脱硝性能。结果表明,活性成分钒和钨绝大多数以非晶态形式存在于载体表面,且具有良好的分散性;主要活性成分V_2O_5负载量越高,脱硝率越高;400℃焙烧温度可以形成催化反应所需的晶相,且维持催化剂较高的比表面积;催化剂低温活性和高温活性是由表面富集和各种成分之间相互作用共同产生的结果,活性组分与载体之间的相互作用对315℃低温脱硝活性影响明显,以先钒后钨负载顺序为宜,表面富集对390℃高温脱硝活性起主要作用,以钒钨同时负载或先钒后钨负载顺序较好;随着m(WO_3)∶m(V_2O_5)的增加,在7.5∶1处催化剂的脱硝率升至最高,随后迅速下降,WO_3负载质量分数以6%为宜。在优化条件V_2O_5负载质量分数0.8%、WO_3负载质量分数6%、先钒后钨负载和400℃焙烧温度下制备了催化剂并进行脱硝性能验证,315℃低温脱硝活性达到69.56%。  相似文献   

18.
Dispersing La2O3 on δ- or γ-Al2O3 significantly enhances the rate of NO reduction by CH4 in 1% O2, compared to unsupported La2O3. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La2O3 precursor used, the pretreatment, and the La2O3 loading. The most active family of catalysts consisted of La2O3 on γ-Al2O3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m2) occurred between the addition of one and two theoretical monolayers of La2O3 on the γ-Al2O3 surface. The best catalyst, 40% La2O3/γ-Al2O3, had a turnover frequency at 700°C of 0.05 s−1, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La2O3/Al2O3 catalysts exhibited stable activity under high conversion conditions as well as high CH4 selectivity (CH4 + NO vs. CH4 + O2). The addition of Sr to a 20% La2O3/γ-Al2O3 sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO=4 to the latter Sr-promoted La2O3/Al2O3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La2O3. Dispersing La2O3 on SiO2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La2O3. This is presumably due to water sensitivity and silicate formation. The La2O3/Al2O3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.  相似文献   

19.
The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al2O3) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir–Hinshelwood (L–H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al2O3 catalysts) on the initial reaction rate. The L–H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al2O3 catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al2O3 or the presulphided NiMo/Al2O3 catalyst.  相似文献   

20.
Effect of additives, In2O3, SnO2, CoO, CuO and Ag, on the catalytic performance of Ga2O3–Al2O3 prepared by sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. As for the reaction in the absence of H2O, CoO, CuO and Ag showed good additive effect. When H2O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga2O3–Al2O3 was depressed considerably, while an intensifying effect of H2O was observed for In2O3- and SnO2-doped Ga2O3–Al2O3. Of several metal oxide additives, In2O3-doped Ga2O3–Al2O3 showed the highest activity for NO reduction by propene in the presence of H2O. Kinetic studies on NO reduction over In2O3–Ga2O3–Al2O3 revealed that the rate-determining step in the absence of H2O is the reaction of NO2 formed on Ga2O3–Al2O3 with C3H6-derived species, whereas that in the presence of H2O is the formation of C3H6-derived species. We presumed the reason for the promotional effect of H2O as follows: the rate for the formation of C3H6-derived species in the presence of H2O is sufficiently fast compared with that for the reaction of NO2 with C3H6-derived species in the absence of H2O. Although the retarding effect of SO2 on the activity was observed for all of the catalysts, SnO2–Ga2O3–Al2O3 showed still relatively high activity in the lower temperature region.  相似文献   

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