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1.
Ni catalysts supported on γ-Al2O3, CeO2 and CeO2–Al2O3 systems were tested for catalytic CO2 reforming of methane into synthesis gas. Ni/CeO2–Al2O3 catalysts showed much better catalytic performance than either CeO2- or γ-Al2O3-supported Ni catalysts. CeO2 as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al2O3 catalysts for this reaction. A weight loading of 1–5 wt% CeO2 was found to be the optimum. Ni catalysts with CeO2 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 CeO2-promoted catalysts are attributed to the oxidative properties of CeO2.  相似文献   

2.
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/Al2O3 catalyst, enhanced partial oxidation activities were observed with the Pd/CeO2/Al2O3, Pd/CeO2/BaO/Al2O3 and Pd/CeO2/BaO/SrO/Al2O3 catalysts. The palladium particles were better dispersed in the presence of CeO2 and SrO. Adding BaO, CeO2 and BaO–CeO2 to γ-Al2O3 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 CeO2/BaO/Al2O3 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 CeO2 promoting the thermal stability of the support, CeO2 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)/CeO2(23)/BaO(11)/SrO(0.8)/Al2O3.  相似文献   

3.
通过制备高纯度的前驱体湃铝石获得了η-Al2O3材料,采用XRD验证了η-Al2O3与γ-Al2O3在晶相结构上的差异,比较了两者的表面形貌、织构及酸碱性能,结果显示,η-Al2O3与γ-Al2O3的比表面积相当,但η-Al2O3具有更弱的弱碱位和较少的强碱位,并拥有丰富的中等强度酸性位。将η-Al2O3与γ-Al2O3作为催化剂应用于CS2水解反应,结果表明,在(200~450) ℃测试温度范围内,η-Al2O3催化剂对CS2的水解活性始终优于γ-Al2O3,两种催化剂上CS2反应的浓度效应也明显不同,推测与它们的酸碱性质影响了对CS2的吸附能力有关,导致两者催化CS2水解反应遵循了不同的机制。  相似文献   

4.
采用浸渍法制备了一系列不同助剂下的负载型Pd/γ-Al2O3催化剂,考察了助剂类型对Pd/γ-Al2O3催化剂一步法合成二甲醚(STD)反应稳定性的影响规律;采用氮吸附、XRD、H2-TPR及TG等多种表征手段考察了稳定性试验前后以及烧炭再生后催化剂的表面物化性质及结构变化。结果表明,助剂成分对Pd/γ-Al2O3催化剂的STD反应稳定性影响显著。相比Pd/γ-Al2O3催化剂,添加CeO2可以提高Pd在γ-Al2O3表面的分散度,但会覆盖表面的部分酸性位,一定程度上提高了催化剂的活性和稳定性,但仍存在Pd烧结和积炭现象;添加复合助剂CeO2-ZrO2后形成的Ce-O-Zr固熔晶面能显著促进Pd均匀分散,提高催化剂的抗积炭能力和抗烧结能力,催化剂的活性和稳定性更高;经SO42-改性后Pd/γ-Al2O3催化剂会因为表面积炭加剧和表面硫流失严重,中强酸酸性位减少而快速失活。CeO2-ZrO2-Pd/γ-Al2O3催化剂经历20h的稳定性试验后CO转化率仍保持59%以上,二甲醚选择性65%以上,烧炭再生后催化活性恢复至新鲜催化剂的91.83%。  相似文献   

5.
In this work, different procedures, namely carbonate coprecipitation and modified solid–solid diffusion, were used to prepare hexaaluminate samples, unsupported or supported onto θ-Al2O3. These samples were used as catalyst for the methane total oxidation as synthesized or after impregnation of 1 wt% Pd. It was observed that the modified solid–solid diffusion procedure is an efficient method to obtain the hexaaluminate structure. At a theoretical ratio x of hexaaluminate onto Al2O3 less than 0.6 (xLa0.2Sr0.3Ba0.5MnAl11O19 + (1−x)·Al2O3, with x = 0.25, 0.60), samples with high specific surface area and θ-Al2O3 structure are then obtained. Large differences in catalytic activity can be observed among the series of sample synthesized. All the pure oxide samples (i.e. without palladium) present low catalytic activity for methane total oxidation compared to a reference Pd/Al2O3 catalyst. The highest activity was obtained for the samples presenting a θ-Al2O3 structure (with x = 0.60) and a high surface area. Impregnation of 1 wt% palladium resulted in an increase in catalytic activity, for all the solids synthesized in this work. Even if the lowest light-off temperature was obtained on the reference sample, similar methane conversions at high temperature (700 °C) were obtained on the stabilized θ-Al2O3 solids (x = 0.25, 0.60). Moreover, the reference sample is found to strongly deactivate with reaction time at the temperature of test (700 °C), due to a progressive reduction of the PdOx active phase into the less active Pd° phase, whereas excellent stabilities in reaction were obtained on the pure and palladium-doped hexaaluminate and supported θ-Al2O3 samples. This clearly showed the beneficial effect of the support for the stabilization of the PdOx active phase at high reaction temperature. These properties are discussed in term of oxygen transfer from the support to the palladium particle. Oxygen transfer is directly related to the Mn3+/Mn2+ redox properties (in the case of the hexaaluminate and stabilized θ-Al2O3 samples), that allows a fast reoxidation of the metal palladium sites since palladium sites reoxidation cannot occur directly by gaseous dioxygen adsorption and dissociation on the surface.  相似文献   

6.
采用浸渍法制备CO偶联制备草酸二甲酯用负载型Pd催化剂,考察载体、浸渍方法、Pd含量、助剂对Pd催化剂性能的影响。根据傅里叶变换红外光谱研究Pd/α-Al_2O_3负载型催化剂上CO偶联制草酸二甲酯的反应机理。结果表明,采用α-Al_2O_3载体,Pd质量分数4‰,掺杂助剂Cu的蛋壳型的Pd/α-Al_2O_3催化剂上,草酸二甲酯时空收率达到735.7 g·(L·h)~(-1)。  相似文献   

7.
Methane combustion over Pd/Al2O3 catalysts with and without added Pt and CeO2 in both oxygen-rich and methane-rich mixtures at temperatures in the range 250–520°C has been investigated using a temperature-programmed reaction procedure with on-line gas analysis (FTIR). During the temperature loop under oxygen-rich conditions, there was an appreciable hysteresis in the activity of unmodified Pd/Al2O3, which was greatly enhanced over Pd–Pt/Al2O3. Over both catalysts the hysteresis was reversed under slightly methane-rich atmospheres, and as temperature was reduced, a sudden collapse or fluctuations in activity were shown respectively over Pd–Pt/Al2O3 and Pd/Al2O3. Such non-steady behaviour was almost eliminated over Pd/Al2O3–CeO2. Under a very narrow range of conditions and over a Pd/Al2O3 packed bed, oscillation of methane combustion was observed.  相似文献   

8.
Two types of NiO/γ-Al2O3 catalysts prepared by the impregnation and the sol–gel method were used for the partial oxidation of methane to syngas at 850°C (GHSV1.8×105 lkg−1 h−1). The effects of the carbon deposition, the loss and sintering of nickel and the phase transformation of γ-Al2O3 support on the catalytic performance during 80 h POM reaction were investigated with a series of characterization such as XRD, BET, AAS, TG, and XPS. The results indicated that the carbon deposition and the loss and sintering of nickel could not cause the serious decrease of catalytic performance over NiO/γ-Al2O3 catalyst during the short-time reaction. However, the slow process of the support γ-Al2O3 phase transforming into -Al2O3 could slowly decrease the performance of NiO/γ-Al2O3 catalysts. Aimed at the reasons of the deactivation, an improved catalyst was obtained by the complexing agent-assisted sol–gel method.  相似文献   

9.
C. Neyertz  M. A. Volpe  C. Gigola   《Catalysis Today》2000,57(3-4):255-260
We have studied the activity and selectivity of Pd/γ-Al2O3, VOx/γ-Al2O3 and Pd–VOx/γ-Al2O3 catalysts for the decomposition of NO and the reduction of NO with CO. Pd–VOx/γ-Al2O3 catalysts were prepared by anchoring Pd(AcAc)2 on VOx/γ-Al2O3. Characterization of the binary samples by hydrogen chemisorption and TPR measurements indicated that the reduction of VOx is enhanced by a close contact with palladium and that partially reduced vanadia decorate noble metal particles. This palladium–vanadium interaction alters the catalytic properties of palladium: the activity for NO decomposition is higher for the binary sample and, for the NO–CO reaction, both the activity and the selectivity to N2 increase when vanadium is in contact with palladium.  相似文献   

10.
汪国辉  刘辉  陈晓蓉  梅华 《工业催化》2014,22(9):709-714
采用等体积浸渍法制备CeO2改性Ni/γ-Al2O3催化剂,通过BET、XRD、H2-TPR和SEM等对催化剂结构及物化性能进行表征,考察Ni-CeO2/γ-Al2O3催化剂对顺酐催化加氢制备丁二酸酐催化性能的影响。结果表明,引入适量CeO2可提高催化剂活性组分Ni的分散度,增加催化剂比表面积,提高催化剂热稳定性。采用负载CeO2质量分数5%的Ni-CeO2/γ-Al2O3催化剂,在反应温度120 ℃、反应压力2.0 MPa和空速0.6 h-1条件下,顺酐转化率为99.5%,丁二酸酐选择性为99.4%。  相似文献   

11.
通过等体积浸渍法制备单贵金属Pt/γ-Al2O3和双金属Pt-Ce/γ-Al2O3催化剂,考察Ce对催化剂活性的影响,确定催化剂最优配比。结果表明,当Pt的负载量为质量分数0.5%时,Pt/γ-Al2O3催化活性最高;当Pt的负载量为质量分数0.2%,Ce的负载量为质量分数1.0%时,Pt-Ce/γ-Al2O3催化剂的催化活性最高。Pt-Ce/γ-Al2O3催化剂的甲苯转化率高于Pt/γ-Al2O3催化剂。随着Pt负载量增大,催化剂孔容、孔径减小。粉体式催化剂性能优于整体式催化剂,但差别不大;Ce的添加有助于催化剂活性的提升。  相似文献   

12.
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   

13.
Reforming of methane with carbon dioxide into syngas over Ni/γ-Al2O3 catalysts modified by potassium, MnO and CeO2 was studied. The catalysts were prepared by impregnation technique and were characterized by N2 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 CeO2 (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 CO2 adsorption, forming a surface reactive carbonate species. Addition of CeO2 or MnO reduced the particle size of nickel, thus increasing Ni dispersion. For Ni–K/CeO2–Al2O3 catalysts, the improved stability was further attributed to the oxidative properties of CeO2. Results of the investigation suggest that stable Ni/Al2O3 catalysts for the carbon dioxide reforming of methane can be prepared by addition of both potassium and CeO2 (or MnO) as promoters.  相似文献   

14.
Ag-modified La0.6Sr0.4MnO3-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al2O3-supported catalysts, Ag/γ-Al2O3, Pt/γ-Al2O3, and Pd/γ-Al2O3. The results showed that the Ag-modified La0.6Sr0.4MnO3-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al2O3 and 0.1%Pt/γ-Al2O3 in the temperature range of 370–573 K. Over a 6%Ag/20%La0.6Sr0.4MnO3/γ-Al2O3 catalyst, the T95 temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al2O3 and 0.1%Pt/γ-Al2O3 catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T95 temperatures. Over a 6%Ag/La0.6Sr0.4MnO3 catalyst, the T95 temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH3CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H2-TPR) and oxygen temperature-programmed desorption (O2-TPD) methods revealed that both the surface and the bulk phase of the perovskite La0.6Sr0.4MnO3 played important roles in the catalytic oxidation of the alcohols, and that γ-Al2O3 as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag+ doped onto the surface of La0.6Sr0.4MnO3 was able to partially occupy the positions of La3+ and Sr2+ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag+ to the surface of La0.6Sr0.4MnO3 resulted in an increase in relative content of the surface O22−/O species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag2O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO3 would also lead to an increase in the content of the reducible Mnn+ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.  相似文献   

15.
Lanthanum-doped Pd/γ-Al2O3 and Pd/γ-Al2O3 membranes were prepared by sol-gel methods. The thermal stability of the unsupported Pd/γ-Al2O3 and La/Pd/γ-Al2O3 membranes was investigated with BET (including average pore size, pore volume and BET surface area), XRD, and DTA techniques. The average pore size of the Pd/γ-Al2O3 membranes increased sharply after sintering at temperatures higher than 1000°C. Addition of 3 mol% lanthanum can raise the temperature of the γ-Al2O3 to-Al2O3 phase transformation significantly. This improves the thermal stability of the Pd/γ-Al2O3 catalytic membranes.  相似文献   

16.
通过采用络合-溶剂热法、水热法和浸渍法三种方法制备了负载量为0.6%(质量分数)的Pd/Al2O3催化剂,重点考察不同制备方法催化氧化间二甲苯作为典型的挥发性有机化合物的能力。结果表明:络合-溶剂热法制备的Pd/Al2O3-com催化剂催化氧化间二甲苯的能力最强,间二甲苯体积分数为0.002%时完全转化温度(T100)为130℃,低于浸渍法制备催化剂的完全转化温度30℃。对Pd/Al2O3催化剂进行了比表面积(BET)、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)等表征分析,发现Pd/Al2O3-com中Pd主要以还原态Pd0高度分散于载体表面,而另两种方法制备的催化剂均有明显的Pd2+存在。结合性能测试及表征分析,表明络合-溶剂热法制备的Pd/Al2O3-com催化剂活性组分Pd的高度分散,增强了催化活性,可满足高浓度间二甲苯、宽气体体积空速条件下催化氧化脱除间二甲苯的工业应用要求。  相似文献   

17.
A series of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H2-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts the surface phase structure were the Ce1−xCuxO2−x solid solution, -Al2O3 and γ-Al2O3. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce1−xCuxO2−x solid solution. The Cu component of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce1−xCuxO2−x solid solution and the Al2O3 washcoats and the FeCrAl support.  相似文献   

18.
Pd/Nb2O5/Al2O3 catalysts were investigated on propane oxidation. Diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) analysis suggested that monolayer coverage was attained between 10 and 20 wt.% of Nb2O5. Temperature programmed reduction (TPR) evidenced the partial reduction of niobium oxide. The maximum propane conversion observed on the Pd/10% Nb2O5/Al2O3 corresponded to the maximum Nb/Al surface ratio. The presence of NbOx polymeric structures near to the monolayer could favor the ideal Pd0/Pd2+ surface ratio to the propane oxidation which could explain the promoting effect of niobium oxide.  相似文献   

19.
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   

20.
For thermodynamic reasons, CO2 has always been considered as inert at mild reaction temperatures (300 °C). In this study, we show that CO2 may be used as a valuable compound for the catalytic combustion of methane (CCM), if ceria-based materials are used as support for the palladium active phase. Adding CO2 in the feed significantly improves performances of ceria-zirconia supported catalysts. On the contrary, catalytic performances are inhibited on Pd/γ-Al2O3. Inhibition can be avoided by mixing the Pd/γ-Al2O3 catalyst with some CeO2 evidencing cooperation phenomena between both catalysts. In situ DRIFTS experiments show that the inhibition of the alumina-supported catalyst is not due to formation of carbonates species. After an in situ reducing pre-treatment, pure CO2 is able to rapidly oxidize reduced Pd/Ce0.21Zr0.79O2 catalyst at 300 °C. Dissociation of CO2 on Ce0.21Zr0.79O2 would be responsible for the oxidation process. Thus, CO2 helps in replenishing the O reservoir (OSC) of the Ce-Zr-O support which is normally consumed by reductants such as CH4, H2 or other HC's. XPS experiments show enrichment in oxygen species bound to Ce (Low BE O1s) on the surface of ceria-zirconia when working in the presence of CO2. Implications of these results on the behavior of ceria-containing catalysts can be important for practical applications, e.g., in automotive exhaust catalysis.  相似文献   

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