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1.
Dispersing La 2O 3 on δ- or γ-Al 2O 3 significantly enhances the rate of NO reduction by CH 4 in 1% O 2, compared to unsupported La 2O 3. 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 La 2O 3 precursor used, the pretreatment, and the La 2O 3 loading. The most active family of catalysts consisted of La 2O 3 on γ-Al 2O 3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m 2) occurred between the addition of one and two theoretical monolayers of La 2O 3 on the γ-Al 2O 3 surface. The best catalyst, 40% La 2O 3/γ-Al 2O 3, 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 La 2O 3/Al 2O 3 catalysts exhibited stable activity under high conversion conditions as well as high CH 4 selectivity (CH 4 + NO vs. CH 4 + O 2). The addition of Sr to a 20% La 2O 3/γ-Al 2O 3 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 La 2O 3/Al 2O 3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La 2O 3. Dispersing La 2O 3 on SiO 2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La 2O 3. This is presumably due to water sensitivity and silicate formation. The La 2O 3/Al 2O 3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications. 相似文献
2.
Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。 相似文献
3.
In this contribution, a commercial spherical SiO 2 was modified with different amounts of La 2O 3, and used as the support of Ni catalysts for autothermal reforming of methane in a fluidized-bed reactor. Nitrogen adsorption, XRD and H 2-TPR analysis indicated that La 2O 3-modified SiO 2 had higher surface area, strengthened interaction between Ni and support, and improved dispersion of Ni. CO 2-TPD found that La 2O 3 increased the alkalescence of SiO 2 and improved the activation of CO 2. Coking reaction (via both temperature-programmed surface reaction of CH 4 (CH 4-TPSR) and pulse decomposition of CH 4) disclosed that La 2O 3 reduced the dehydrogenation ability of Ni. CO 2-TPO, O 2-TPO (followed after CH 4-TPSR) confirmed that only part amount of carbon species derived from methane decomposition could be removed by CO 2, and O 2 in feed played a crucial role for the gasification of the inactive surface carbons. Ni/ xLa 2O 3-SiO 2 ( x = 10, 15, 30) possessed high activity and excellent stability for autothermal reforming of methane in a fluidized-bed reactor. 相似文献
4.
The mechanism of the CO 2 reforming of methane reaction over the Pt/ZrO 2 catalyst was investigated using a temporal analysis of products (TAP) reactor system. For comparative purposes, the reaction pathway using a Pt/Al 2O 3 catalyst was also examined. A reaction sequence is suggested for both catalysts. Over both catalysts, methane decomposition takes place over platinum. The main difference between the two catalysts concerns the carbon dioxide dissociation. Over Pt/Al 2O 3 this step is assisted by hydrogen. Over Pt/ZrO 2 this step takes place over the zirconia support and involves surface vacancies. Moreover, large pools of formate and carbonate species are present on the zirconia. Transient studies conducted to determine the origin of carbon species accumulated during CO 2 reforming revealed that more than 99% of the carbon was derived from the methane molecule over both catalysts. Over the Pt/ZrO 2 catalyst, only a single very reactive carbon species was detected, while over the Pt/Al 2O 3 a second less active species was also formed. 相似文献
5.
The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V 2O 5/Al 2O 3 catalysts was investigated. The Pd/V 2O 5/Al 2O 3 catalysts were more active than V 2O 5/Al 2O 3 and Pd/Al 2O 3 catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V 4+ species were more active, the Pd particle size effect was responsible for the higher activity. 相似文献
6.
MgO-promoted Ni/Al 2O 3 catalysts have been investigated with respect to catalytic activity and coke formation in combined steam and carbon dioxide reforming of methane (CSCRM) to develop a highly active and stable catalyst for gas to liquid (GTL) processes. Ni/Al 2O 3 catalysts were promoted through varying the MgO content by the incipient wetness method. X-ray diffraction (XRD), BET surface area, H 2-temperature programmed reduction (TPR), H 2-chemisorption and CO 2-temperature programmed desorption (TPD) were used to observe the characteristics of the prepared catalysts. The coke formation and amount in used catalysts were examined by SEM and TGA, respectively. H 2/CO ratio of 2 was achieved in CSCRM by controlling the feed H 2O/CO 2 ratio. The catalysts prepared with 20 wt.% MgO exhibit the highest catalytic performance and have high coke resistance in CSCRM. MgO promotion forms MgAl 2O 4 spinel phase, which is stable at high temperatures and effectively prevents coke formation by increasing the CO 2 adsorption due to the increase in base strength on the surface of catalyst. 相似文献
7.
以碱共沉淀法制备Mg-Al水滑石,然后采用浸渍法负载活性组分Pt,经焙烧、氢气还原得到Pt/Al_2O_3与Pt/Mg O-Al_2O_3催化剂,采用XRD、N2吸附-脱附、FT-IR、H2-TPR和Py-IR等分析Mg O的加入对Pt/Al_2O_3催化剂结构性能的影响,并在甲基环己烷连续脱氢反应中对比两种催化剂活性。结果表明,Pt/Mg O-Al_2O_3催化剂比表面积小于Pt/Al_2O_3催化剂,且表面基本无酸性活性中心,但表现出与Pt/Al_2O_3催化剂相同的脱氢活性。在Pt负载质量分数2%、催化剂用量0.5 g、甲基环己烷0.1 m L·min-1纯样进料和325℃反应10 h后,原料平均转化率79.9%,脱氢产物只有甲苯,对应的产氢速率192.8 mmol·(g-metal·min)-1,表现出优良的脱氢活性。 相似文献
8.
The role of La 2O 3 loading in Pd/Al 2O 3-La 2O 3 prepared by sol–gel on the catalytic properties in the NO reduction with H 2 was studied. The catalysts were characterized by N 2 physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO. The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La2O3 inclusion. The selectivity depends on the NO/H2 molar ratio (GHSV = 72,000 h−1) and the extent of interaction between Pd and La2O3. At NO/H2 = 0.5, the catalysts show high N2 selectivity (60–75%) at temperatures lower than 250 °C. For NO/H2 = 1, the N2 selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H2O vapor. The high N2 selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdOx phase interacting with La2O3. The formation of this phase is favored by the spreading of PdO promoted by La2O3. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al2O3 the O2 uptake is consistent with the oxidation of PdO to PdO2, and when La2O3 is present the O2 uptake exceeds that amount (1.5 times). La2O3 in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N2. 相似文献
9.
A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NO x adsorber catalyst, Pt/K/Al 2O 3, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al 2O 3 phase with associated hydroxyl groups at the surface, and an alkalized-Al 2O 3 phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al 2O 3 and 65% for the alkalized-Al 2O 3. NO 2 and CO 2 chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al 2O 3 adsorbs 0.087 μmol CO 2/m 2and 2.0 μmol NO 2/m 2, and Pt/K/Al 2O 3 adsorbs 2.0 μmol CO 2/m 2and 6.4 μmol NO 2/m 2. This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al 2O 3 during both lean and rich periods of the NO x adsorber catalyst cycle. 相似文献
10.
The surface properties of a series of V 2O 5 catalysts supported on different oxides (Al 2O 3, H–Na/Y zeolite, MgO, SiO 2, TiO 2 and ZrO 2) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH 3 adsorption. In the case of the V 2O 5/SiO 2 system TEM images evidenced the presence of V 2O 5 crystallites, whereas such segregated phase was not observed for the other samples. VO x species resulted widely spread on the surface of Al 2O 3, H–Na/Y zeolite, MgO and SiO 2, whereas on TiO 2 and ZrO 2 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 V 2O 5/TiO 2 and V 2O 5/ZrO 2 catalysts. 相似文献
11.
It is shown that introduction of additives of rare-earth element oxides (La 2O 3, CeO 2) enables regulating the structural and functional characteristics of Pd/Al 2O 3-catalysts (applied on ceramic monoliths of honeycomb structure) of nitrogen oxide reduction by methane. Modifying additives provide increase of thermal stability of porous structure of both highly dispersed Al 2O 3, as the second support, and the catalyst as a whole. Contribution of La2O3 and CeO2 in increasing the thermal stability is of an additive nature, and lanthanum oxide shows the higher efficiency than cerium one. According to X-ray phase analysis data, stabilizing action is conditioned by occurrence of rare-earth element oxides into lattice of Al2O3, which retards diffusional processes leading to phase transitions of low-temperature crystalline modifications of alumina into high-temperature ones with a low specific surface. For the catalyst samples modified with La2O3 an effect of thermal activation is observed, which is revealed by increase in catalytic activity as a result of annealing at 850 °C. Such a phenomenon, as shown by means of X-ray photoelectron spectroscopy technique, can be explained via stabilization of palladium in singly charged state in the form of groups of Pd+O2− and corresponding increase in concentration of active centers. 相似文献
12.
Mixed oxides of alumina and zirconia having a relative composition of 50, 80 and 100% Zr 2O were synthesized by means of sol–gel methods. The catalysts were sulfated with H 2SO 4 1N, and were loaded with 0.3% Pt metal using the incipient wetness technique. The characterization of the physicochemical properties was carried out using XRD, N 2-adsorption at 78 K, and SEM. The catalytic properties of the Al 2O 3–ZrO 2 series were studied by means of dehydration of 2-propanol at 180°C and isomerization of n-hexane at 250°C, 1 atm. The sulfated solids presented a high surface acidity and a limited crystallinity, together with high activity for alcohol dehydration (i.e. 2-propanol). On the other hand, the Al 2O 3–ZrO 2 solid solutions (i.e. those having a 20–80% composition) turned out to be the most active ones for the isomerization of n-hexane. 相似文献
13.
A multi-component NO x-trap catalyst consisting of Pt and K supported on γ-Al 2O 3 was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H 2O and CO 2 on NO x storage. The Al 2O 3 support was shown to have NO x trapping capability with and without Pt present (at 250 °C Pt/Al 2O 3 adsorbs 2.3 μmols NO x/m 2). NO x is primarily trapped on Al 2O 3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO x/m 2, and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al 2O 3 catalyst are coordinated on the Al 2O 3 support at saturation. When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%. Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3 destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition. 相似文献
14.
The phase diagram of the Al 2O 3–ZrO 2–Nd 2O 3 system was constructed in the temperature range 1250–2800 °C. The liquidus surface of the phase diagram reflects the preferentially eutectic interaction in the system. Two new ternary and one new binary eutectics were found. The minimum melting temperature is 1675 °C and it corresponds to the ternary eutectic Nd 2O 3·11Al 2O 3 + F-ZrO 2 + NdAlO 3. The solidus surface projection and the schematic of the alloy crystallization path confirm the preferentially congruent character of phase interaction in the ternary system. The polythermal sections present the complete phase diagram of the Al 2O 3–ZrO 2–Nd 2O 3 system. No ternary compounds or regions of remarkable solid solution were found in the components or binaries in this ternary system. 相似文献
15.
Supported molybdenum and tungsten carbides were synthesized by temperature-programmed reactions. These materials were characterized by XRD, EDS analysis, HRTEM and CO chemisorption. Hydrogenation of tetralin was carried out at a total pressure of 4 MPa (3.06 MPa of H 2), at 573 K, without or with sulfur (200 ppm of sulfur as DMDS). The resulting activities were compared with those of MoS 2/Al 2O 3 and Pt (1% (w/w) metal loading) supported on Al 2O 3 or SiO 2. In the absence of sulfur, WC/Al 2O 3 showed an initial activity similar to that of Pt/SiO 2, higher than that of MoS 2/Al 2O 3 but lower than that of Pt/Al 2O 3. In the presence of H 2S, WC/Al 2O 3 showed a steady-state activity similar to that of Pt/Al 2O 3 (which suffered a marked deactivation). Post-reaction characterization did not show any sulfur poisoning of the supported carbides. Therefore the supported carbides are sulfur-tolerant and promising catalysts for the hydrogenation of aromatics in diesel fuels in the presence of small amounts of S-containing compounds. 相似文献
16.
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
17.
The NiSO 4 supported on Fe 2O 3-promoted ZrO 2 catalysts were prepared by the impregnation method. Fe 2O 3-promoted ZrO 2 was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and iron nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt.%, indicating good dispersion of nickel sulfate on the surface of Fe 2O 3–ZrO 2. The addition of nickel sulfate (or Fe 2O 3) to ZrO 2 shifted the phase transition of ZrO 2 (from amorphous to tetragonal) to higher temperatures because of the interaction between nickel sulfate (or Fe 2O 3) and ZrO 2. 15-NiSO 4/5-Fe 2O 3–ZrO 2 containing 15 wt.% NiSO 4 and 5 mol% Fe 2O 3, and calcined at 500 °C exhibited a maximum catalytic activity for ethylene dimerization. NiSO 4/Fe 2O 3–ZrO 2 catalysts was very effective for ethylene dimerization even at room temperature, but Fe 2O 3–ZrO 2 without NiSO 4 did not exhibit any catalytic activity at all. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The addition of Fe 2O 3 up to 5 mol% enhanced the acidity, surface area, thermal property, and catalytic activities of catalysts gradually, due to the interaction between Fe 2O 3 and ZrO 2 and due to consequent formation of Fe–O–Zr bond. 相似文献
18.
CH 4/CO 2 reforming over La 2NiO 4 and 10%NiO/CeO 2–La 2O 3 catalysts under the condition of supersonic jet expansion was studied via direct monitoring of the reactants and products using the sensitive technique of cavity ring-down spectroscopy. Vibration–rotational absorption lines of CH 4, H 2O, CO 2 and CO molecules were recorded in the near infrared spectral region. Our results indicated that La 2NiO 4 is superior to 10%NiO/CeO 2–La 2O 3 in performance. In addition, we observed enhanced reverse-water-gas-shift reaction at augmented reaction temperature. The formation of reaction intermediates was also investigated by means of time-of-flight mass spectrometry and there was the detection of CH x+, OH + and H + species. 相似文献
19.
Al 2O 3–SiO 2 mixed oxide has been investigated as a support for hydrotreating catalyst with variation of its composition [Si/(Si + Al) = 0.06, 0.12, 0.31, 0.56, 0.78] and its interaction with the surface active metals (NiMo). The composition of support and surface species (NiMo) of catalysts were characterized by specific surface area, atomic absorption, SEM-EDX, XRD, temperature programmed reduction (TPR), Raman analysis, scanning electron microscopy (STEM) and transmission electron microscopy (TEM). Incorporation of SiO 2 in Al 2O 3 promotes a weak interaction between the active phases and particularly catalyst that predominated with SiO 2 content. The oxide and sulfided catalysts characterization indicated that the effect of support is responsible to form different catalytic sites. Crystallization of MoO 3 phases and a relatively longer crystal of MoS 2 in the sulfided catalyst were attributed to an increasing SiO 2 content in the support. The catalytic behavior of the NiMo supported catalysts is explained in terms of structural changes on the surface due to the support and active metal interactions. The activity of the different catalysts evaluated in the thiophene hydrodesulfurization reaction was higher for the catalyst having lower SiO 2 content in the support. 相似文献
20.
A mean field model, for storage and desorption of NO x in a Pt/BaO/Al 2O 3 catalyst is developed using data from flow reactor experiments. This relatively complex system is divided into five smaller sub-systems and the model is divided into the following steps: (i) NO oxidation on Pt/Al 2O 3; (ii) NO oxidation on Pt/BaO/Al 2O 3; (iii) NO x storage on BaO/Al 2O 3; (iv) NO x storage on Pt/BaO/Al 2O 3 with thermal regeneration and (v) NO x storage on Pt/BaO/Al 2O 3 with regeneration using C 3H 6. In this paper, we focus on the last sub-system. The kinetic model for NO x storage on Pt/BaO/Al 2O 3 was constructed with kinetic parameters obtained from the NO oxidation model together with a NO x storage model on BaO/Al 2O 3. This model was not sufficient to describe the NO x storage experiments for the Pt/BaO/Al 2O 3, because the NO x desorption in TPD experiments was larger for Pt/BaO/Al 2O 3, compared to BaO/Al 2O 3. The model was therefore modified by adding a reversible spill-over step. Further, the model was validated with additional experiments, which showed that NO significantly promoted desorption of NO x from Pt/BaO/Al 2O 3. To this NO x storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO 2 and C 3H 6. The main reactions for continuous reduction of NO x occurs on Pt by reactions between hydrocarbon species and NO in the model. The model is also able to describe the reduction phase, the storage and NO breakthrough peaks, observed in experiments. 相似文献
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