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1.
Noble metal (Rh, Pt, Pd, Ir, Ru, and Ag) and Ni catalysts supported on CeO 2–Al 2O 3 were investigated for water gas shift reaction at ultrahigh temperatures. Pt/CeO 2–Al 2O 3 and Ru/CeO 2–Al 2O 3 demonstrated as the best catalysts in terms of activity, hydrogen yield and hydrogen selectivity. At 700 °C and steam to CO ratio of 5.2:1, Pt/CeO 2–Al 2O 3 converted 76.3% of CO with 94.7% of hydrogen selectivity. At the same conditions, the activity and hydrogen selectivity for Ru/CeO 2–Al 2O 3 were 63.9% and 85.6%, respectively. Both catalysts showed a good stability over 9 h of continuous operation. However, both catalysts showed slight deactivation during the test period. The study revealed that Pt/CeO 2–Al 2O 3 and Ru/CeO 2–Al 2O 3 were excellent ultrahigh temperature water gas shift catalysts, which can be coupled with biomass gasification in a downstream reactor. 相似文献
2.
The catalytic performance of supported noble metal catalysts for the steam reforming (SR) of ethanol has been investigated in the temperature range of 600–850 °C with respect to the nature of the active metallic phase (Rh, Ru, Pt, Pd), the nature of the support (Al 2O 3, MgO, TiO 2) and the metal loading (0–5 wt.%). It is found that for low-loaded catalysts, Rh is significantly more active and selective toward hydrogen formation compared to Ru, Pt and Pd, which show a similar behavior. The catalytic performance of Rh and, particularly, Ru is significantly improved with increasing metal loading, leading to higher ethanol conversions and hydrogen selectivities at given reaction temperatures. The catalytic activity and selectivity of high-loaded Ru catalysts is comparable to that of Rh and, therefore, ruthenium was further investigated as a less costly alternative. It was found that, under certain reaction conditions, the 5% Ru/Al 2O 3 catalyst is able to completely convert ethanol with selectivities toward hydrogen above 95%, the only byproduct being methane. Long-term tests conducted under severe conditions showed that the catalyst is acceptably stable and could be a good candidate for the production of hydrogen by steam reforming of ethanol for fuel cell applications. 相似文献
3.
The reaction of ethanol for the production of hydrogen has been studied over a series of metal supported CeO 2 catalysts. The study is conducted by TPD, steady state reaction, XPS, TEM, and infrared spectroscopy. TPD gave evidence for the role of Rh in dissociating the carbon–carbon bond needed for efficient production of hydrogen molecules. IR of CO adsorption at 90 K revealed that Rh particles are most likely in very small clusters as evidenced by a single OC–Rh IR band at 2020 cm −1. TEM did not show conclusive evidence for the presence of the metal on-top of the CeO 2 support, yet the Rh-Pd/CeO 2 used catalyst has features that might be attributed to epitaxial growth of the noble metal along the (1 1 1) surface of the CeO 2 support. Considerable reconstruction of the CeO 2 support is seen for the used catalysts, in addition. Reforming of ethanol to hydrogen using (3 moles of water per mole of ethanol) was very efficient particularly above 650 K where hydrogen selectivity reaches 60 vol.%. At these temperatures hydrogen production from reforming of methane takes place. 相似文献
4.
Supported base metal catalysts were tested for the preferential oxidation of CO (CO PROX). The catalysts we investigated covered a wide range of transition metals (Co, Cr, Cu, Ni, Zn) supported on oxides with very different acidic, basic and redox properties (MgO, La 2O 3, SiO 2–Al 2O 3, CeO 2, Ce 0.63Zr 0.37O 2). The influence of the metal loading (Cu), the support properties (acidity, basicity, redox, surface area) and the reaction conditions (reaction temperature, feed composition) on the catalyst activity and selectivity was evaluated. The activity of ceria and ceria–zirconia supported copper catalysts was comparable to the performances of noble metal samples classically used for the PROX reaction. In addition, Cu–CeO 2 catalysts showed a practically constant and high selectivity towards CO oxidation in the temperature range of 50–150 °C. Due to the strong synergetic effect between copper and ceria, only a small amount of copper (0.3 wt.%) was necessary to get an active catalyst. The best catalytic performances were obtained for the samples containing 1–3 wt.% copper. The presence of small copper particles in close interaction with the ceria support was shown to be responsible for the enhanced activity. Except for the hydrogen oxidation, no parallel reactions (CO or CO 2 methanation reactions, coking, RWGS) could be detected over these catalysts. Classically, an increase of the oxygen excess led to an increased CO conversion with a simultaneous loss of selectivity towards CO 2. Finally, the presence of CO 2 in the feed negatively affected the catalytic activity. This effect was attributed to the adsorption of CO 2 on the copper sites, probably as CO. 相似文献
5.
The catalytic activity of supported noble metal catalysts (Pt, Rh, Ru, and Pd) for the WGS reaction is investigated with respect to the physichochemical properties of the metallic phase and the support. It has been found that, for all metal-support combinations investigated, Pt is much more active than Pd, while Rh and Ru exhibit intermediate activity. The turnover frequency (TOF) of CO conversion does not depend on metal loading, dispersion or crystallite size, but depends strongly on the nature of the metal oxide carrier. In particular, catalytic activity of Pt and Ru catalysts, is 1-2 orders of magnitude higher when supported on “reducible” (TiO 2, CeO 2, La 2O 3, and YSZ) rather than on “irreducible” (Al 2O 3, MgO, and SiO 2) metal oxides. In contrast to what has been found in our previous study over Pt/TiO 2 catalysts, catalytic activity of dispersed Pt does not depend on the structural and morphological characteristics of CeO 2, such as specific surface area or primary crystallite size. 相似文献
6.
Ni catalysts supported on γ-Al 2O 3, CeO 2 and CeO 2–Al 2O 3 systems were tested for catalytic CO 2 reforming of methane into synthesis gas. Ni/CeO 2–Al 2O 3 catalysts showed much better catalytic performance than either CeO 2- or γ-Al 2O 3-supported Ni catalysts. CeO 2 as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO 2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al 2O 3 catalysts for this reaction. A weight loading of 1–5 wt% CeO 2 was found to be the optimum. Ni catalysts with CeO 2 promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO 2-promoted catalysts are attributed to the oxidative properties of CeO 2. 相似文献
7.
In the steam gasification of biomass, the additive effect of noble metals such as Pt, Pd, Rh and Ru to the Ni/CeO 2/Al 2O 3 catalyst was investigated. Among these noble metals, the addition of Pt was most effective even when the loading amount of added Pt was as small as 0.01 wt.%. In addition, the catalyst characterization suggests the formation of the Pt–Ni alloy over the Pt/Ni/CeO 2/Al 2O 3. 相似文献
8.
In this paper, Co 3O 4/CeO 2 catalysts for steam reforming of ethanol (SRE) were prepared by co-precipitation and impregnation methods. The catalysts prepared by co-precipitation were very active and selective for SRE. Over 10%Co 3O 4/CeO 2 catalyst, ethanol conversion was close to 100% and hydrogen selectivity was about 70% at 450 °C. The catalysts were characterized by X-ray diffraction, temperature-programmed reduction (TPR) and BET surface area measurements. The preparation method influenced the interaction between cobalt and CeO 2 evidently. The incorporation of Co ions into CeO 2 crystal lattice resulted in weaker interaction between cobalt and ceria on catalyst surface. In comparison with catalysts prepared by impregnation, more cobalt ions entered into CeO 2 lattice, and resulted in weaker interaction between active phase and ceria on surface of Co 3O 4/CeO 2 prepared by co-precipitation. Thus, cobalt oxides was easier to be reduced to metal cobalt which was the key active component for SRE. Meanwhile, the incorporation of Co ions into CeO 2 crystal lattice was beneficial for resistance to carbon deposition. 相似文献
9.
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 CeO 2 and Al 2O 3 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/CeO 2 catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al 2O 3 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/Al 2O 3 catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O 2/CO ratio due to the oxidation of H 2 which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO 2 showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O 2/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al 2O 3, CuO/CeO 2), 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
10.
The effect of CeO 2 loading (1–20 wt.%) on the properties and catalytic behaviors of CeO 2–Al 2O 3-supported Pt catalysts on the partial oxidation of methane was studied. The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC). XRD and TPR results showed that the pretreatment temperature of the support influences on the amount of CeO 2 with fluorite structure. The pretreatment temperature of the support and CeO 2 loading influenced the morphology of Pt. OSC analysis showed a significant increase in the oxygen storage capacity per weight of CeO 2 for samples with high CeO 2 loading (12 and 20 wt.%). TPR analyses showed that the addition of Pt promotes the reduction of CeO 2. This effect was more significant for the catalysts with high CeO 2 loading (≥12 wt.%). The dispersion of Pt, measured by the rate of cyclohexane dehydrogenation, increases with increasing of the pretreatment temperature of the support. It was shown that the kind of the support is very important for obtaining of catalysts resistant to carbon formation. The catalysts with high CeO 2 loading (≥12 wt.%) showed the highest catalytic activity and stability in the reaction of partial oxidation of methane due to a higher Pt–CeO 2 interface. 相似文献
11.
In many of the applications of catalytic combustion small amounts of sulphur compounds are present in the feed gas. In the case of natural gas combustion, and solid fuel syngas, the sulphur compounds are in reduced forms. The present work investigates the influence of small quantities of reduced sulphur compounds on the combustion of methane over alumina-supported precious metal catalysts. The kinetics of the methane combustion in the presence of low concentrations of a mixture of sulphur compounds (ethyl mercaptan, methyl mercaptan, carbonyl sulphide and hydrogen sulphide) are compared with those in the absence of sulphur compounds. The ease of regeneration of the poisoned catalysts, via low temperature reduction with hydrogen, is also examined. In the conditions studied all catalysts have reduced activity in the presence of the sulphur-based gas mixture, but Pt/Al 2O 3 and Rh/Al 2O 3 are more strongly poisoned than Pd/Al 2O 3. Qualitative studies using gas chromatography with atomic emission detection of the exhaust gases, and FTIR spectroscopy of the spent Rh/Al 2O 3 catalyst, suggest that the catalysts experience a mixture of reduced and oxidised species under reaction conditions, and that sulphating of the support occurs. The regeneration step facilitates metal mobility and meets with varying success depending upon the metal. Pt/Al 2O 3 in particular is difficult to regenerate by reduction in hydrogen (400 °C for 0.5 h), and agglomeration is observed by TEM. Rh/Al 2O 3 regenerates well, and low metal particle size is maintained. A non-linear deactivation model is tested to separate sulphur-induced deactivation from ‘natural’ deactivation in the reaction mixture and preliminary results are presented. 相似文献
12.
The catalytic performance of Pt and Rh catalysts for the selective catalytic reduction (SCR) of NO by propylene in the presence of excess oxygen has been investigated over catalysts supported on six different metal oxide carriers (CeO 2, Al 2O 3, TiO 2, YSZ, ZrO 2 and W 6+-doped TiO 2). It has been found that the nature of the dispersed metal affects strongly the light-off temperature of propylene, the maximum NO conversion to reduction products and the selectivity towards nitrogen. For a given support, Pt catalysts are always more active for both NO reduction and propylene oxidation, but are much less selective towards N 2, compared to Rh catalysts. Rhodium catalysts are able to selectively reduce NO even in the absence of oxygen in the feed. However, their activity is suppressed with increasing oxygen feed concentration possibly due to the formation of less reactive rhodium oxides. In contrast, oxygen promotes the de-NO x activity of platinum catalysts but decreases selectivity towards nitrogen. Results are explained by considering the effects of the nature of the metallic phase and the support on the elementary steps of the propylene-SCR reaction. It is concluded that the catalytic performance of both metals may be improved by proper selection of the support. 相似文献
13.
A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performances of these catalysts for the steam reforming of methanol were evaluated in a laboratory-scale fixed-bed reactor at 0.1 MPa and temperatures between 473 and 543 K. The results showed that the catalytic activity depended greatly on the catalyst reducibility and the specific surface area of Cu. An approximate linear correlation between the catalytic activity and the Cu surface area was found for all catalysts investigated in this study.Compared to CuO/ZnO/Al_2O_3, the ZrO_2-doped CuO/ZnO/Al_2O_3 exhibited higher activity and selectivity to CO,while the CeO_2-doped catalyst displayed lower activity and selectivity. Finally, an intrinsic kinetic study was carried out over a screened CuO/ZnO/CeO_2/Al_2O_3 catalyst in the absence of internal and external mass transfer effects. A good agreement was observed between the model-derived effluent concentrations of CO(CO_2) and the experimental data. The activation energies for the reactions of methanol-steam reforming, water-gas shift and methanol decomposition over CuO/ZnO/CeO_2/Al_2O_3 were 93.1, 85.1 and 116.5 k J·mol~(-1), respectively. 相似文献
14.
由丙烷直接催化脱氢制取丙烯已经成为增产丙烯的重要手段之一。以水热法制备Al_2O_3载体,采用等体积浸渍法制备不同PtSn负载量的PtSn/Al_2O_3催化剂。通过XRD、N2-吸附、拉曼光谱和H2-TPR等对其进行表征,并考察不同PtSn负载量对催化剂催化丙烷脱氢性能的影响。结果表明,在制备的催化剂中,Pt1.5Sn3/Al_2O_3具有最高的催化丙烷脱氢活性和稳定性,丙烷初始转化率高达55.6%,丙烯选择性98.1%。反应330 min后,丙烷转化率仅降约10%,选择性保持不变。 相似文献
15.
The formation of surface species in the ethanol–water interaction and the reforming of ethanol have been investigated on Pt/Al 2O 3 catalysts and for comparison on the support. By means of infrared spectroscopy it was found that on Pt/Al 2O 3 not only adsorbed ethanol, different types of ethoxy species but also traces of acetaldehyde and a significant amount of acetate groups were detectable on the surface. The latter species were stable even at 700 K. The gas phase analysis of the ethanol-dosed surface showed at higher temperature considerable amount of ethylene in the case of Al 2O 3 and hydrogen in the case of Pt/Al 2O 3. In the ethanol + water reaction the selectivity of H2 and CO2 formation at 723 K decreased in time, while that of ethylene increased. This trend was attenuated by increasing the following parameters: water concentration, metal loading and reaction temperature. It was assumed that this behavior of Pt/Al2O3 in the ethanol + water reaction can be attributed to the formation of surface acetate groups which hindered the reaction on the metal, although these species were located rather on the support. 相似文献
16.
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
17.
Four different modifications of alumina were prepared for use as the support for a Pd catalyst used for the partial oxidation of methane to syngas. The catalysts were washcoated on a metallic monolith in order to determine their activities at high gas flow rates. Compared with the Pd/Al 2O 3 catalyst, enhanced partial oxidation activities were observed with the Pd/CeO 2/Al 2O 3, Pd/CeO 2/BaO/Al 2O 3 and Pd/CeO 2/BaO/SrO/Al 2O 3 catalysts. The palladium particles were better dispersed in the presence of CeO 2 and SrO. Adding BaO, CeO 2 and BaO–CeO 2 to γ-Al 2O 3 prevented the transformation of the alumina phase during the 3-day aging process at 1000 °C, providing the support with some level of thermal stability. The addition of small amounts of SrO to the CeO 2/BaO/Al 2O 3 support enhanced the thermal stability of the Pd particles and minimized their sintering. The triply promoted Pd catalyst studied in this work was effective in carrying out partial oxidation at high temperatures, with BaO and CeO 2 promoting the thermal stability of the support, CeO 2 and SrO dispersing the Pd particles and SrO anchoring the Pd particles strongly to the support. The composition of the catalyst which gave both the highest partial oxidation activity and the best thermal stability was Pd(2)/CeO 2(23)/BaO(11)/SrO(0.8)/Al 2O 3. 相似文献
18.
The capability of flame-made Rh/Ce 0.5Zr 0.5O 2 nanoparticles catalyzing the production of H 2- and CO-rich syngas from butane was investigated for different Rh loadings (0–2.0 wt% Rh) and two different ceramic fibers (Al 2O 3/SiO 2 and SiO 2) as plugging material in a packed bed reactor for a temperature range from 225 to 750 °C. The main goal of this study was the efficient processing of butane at temperatures between 500 and 600 °C for a micro-intermediate-temperature SOFC system. Our results showed that Rh/Ce 0.5Zr 0.5O 2 nanoparticles offer a very promising material for butane-to-syngas conversion with complete butane conversion and a hydrogen yield of 77% at 600 °C. The catalytic performance of packed beds strongly depended on the use of either Al 2O 3/SiO 2 or SiO 2 fiber plugs. This astonishing effect could be attributed to the interplay of homogeneous and heterogeneous chemical reactions during the high-temperatures within the reactor. 相似文献
19.
Reforming of methane with carbon dioxide into syngas over Ni/γ-Al 2O 3 catalysts modified by potassium, MnO and CeO 2 was studied. The catalysts were prepared by impregnation technique and were characterized by N 2 adsorption/desorption isotherm, BET surface area, pore volume, and BJH pore size distribution measurements, and by X-ray diffraction and scanning electron microscopy. The performance of these catalysts was evaluated by conducting the reforming reaction in a fixed bed reactor. The coke content of the catalysts was determined by oxidation conducted in a thermo-gravimetric analyzer. Incorporation of potassium and CeO 2 (or MnO) onto the catalyst significantly reduced the coke formation without significantly affecting the methane conversion and hydrogen yield. The stability and the lower amount of coking on promoted catalysts were attributed to partial coverage of the surface of nickel by patches of promoters and to their increased CO 2 adsorption, forming a surface reactive carbonate species. Addition of CeO 2 or MnO reduced the particle size of nickel, thus increasing Ni dispersion. For Ni–K/CeO 2–Al 2O 3 catalysts, the improved stability was further attributed to the oxidative properties of CeO 2. Results of the investigation suggest that stable Ni/Al 2O 3 catalysts for the carbon dioxide reforming of methane can be prepared by addition of both potassium and CeO 2 (or MnO) as promoters. 相似文献
20.
The study of catalytic decomposition of nitrous oxide to nitrogen and oxygen over Rh catalysts supported on various supports (USY, NaY, Al 2O 3, ZrO 2, FSM-16, CeO 2, La 2O 3) showed that the activities of Rh/Al 2O 3 and Rh/USY (ultrastable Y zeolite) catalysts were comparable to or higher than the other catalysts reported in the literatures. The catalytic activity of N 2O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. A pulsed N 2O experiment over a Rh/USY catalyst suggested that the catalytic N 2O decomposition occurs on oxygen-covered surface and that O 2 may be freed on collision of N 2O molecules with the adsorbed oxygen atoms. 相似文献
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