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1.
Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO2-doped Ga2O3–Al2O3 prepared by sol–gel method. Although SnO2-doped Ga2O3–Al2O3 gave lower NO conversion than Ga2O3–Al2O3 in the absence of H2O, the activity was enhanced considerably by the presence of H2O and much higher than that of Ga2O3–Al2O3. The presence of SnO2 and Ga2O3–Al2O3 species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H2O. The promotional effect of H2O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H2O. The other is the selective inhibition by H2O of the reaction steps resulting in propene oxidation to COx without reducing NO.  相似文献   

2.
An In2O3/Al2O3 catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO2 in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NOX adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO2, and the amount of ad-NO3 species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO2 enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO2 at low temperature, because active C3H6 (partially oxidized C3H6) is crucial at low temperature.  相似文献   

3.
Catalytic properties of supported gallium oxides have been examined for the selective reduction of NO by CH4 in excess oxygen. The activity was greatly affected by the support; Ga2O3/Al2O3 (Al2O3 supported Ga2O3) and Ga2O3–Al2O3 mixed oxide exhibited high activity and selectivity as comparable to Ga-ZSM-5, while unsupported Ga2O3 and the other supported Ga2O3 were ineffective. For Ga2O3/Al2O3, the activity changed with Ga2O3 content, and was highest at about 30 wt% Ga2O3, which corresponds to a theoretical monolayer coverage. Gallium oxide highly dispersed on Al2O3 is considered to be responsible for the high activity and selectivity. The reaction characteristics of Ga2O3/Al2O3 were studied and compared with Ga-ZSM-5 and Co-ZSM-5. Ga2O3/Al2O3 exhibited the highest activity and selectivity at high temperature. In addition, Ga2O3/Al2O3 showed higher tolerance against water than Ga-ZSM-5. C3H8 and C3H6 were also evaluated as reducing agents, and Ga2O3/Al2O3 showed higher activity than Ga-ZSM-5 above 723 K achieving almost complete reduction of NO to N2.  相似文献   

4.
Mixed oxides of alumina and zirconia having a relative composition of 50, 80 and 100% Zr2O were synthesized by means of sol–gel methods. The catalysts were sulfated with H2SO4 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, N2-adsorption at 78 K, and SEM. The catalytic properties of the Al2O3–ZrO2 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 Al2O3–ZrO2 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   

5.
Ag-based catalysts supported on various metal oxides, Al2O3, TiO2, and TiO2–Al2O3, were prepared by the sol–gel method. The effect of SO2 on catalytic activity was investigated for NO reduction with propene under lean burn condition. The results showed the catalytic activities were greatly enhanced on Ag/TiO2–Al2O3 in comparison to Ag/Al2O3 and Ag/TiO2, especially in the low temperature region. Application of different characterization techniques revealed that the activity enhancement was correlated with the properties of the support material. Silver was highly dispersed over the amorphous system of TiO2–Al2O3. NO3 rather than NO2 or NOx reacted with the carboxylate species to form CN or NCO. NO2 was the predominant desorption species in the temperature programmed desorption (TPD) of NO on Ag/TiO2–Al2O3. More amount of formate (HCOO) and CN were generated on the Ag/TiO2–Al2O3 catalyst than the Ag/Al2O3 catalyst, due to an increased number of Lewis acid sites. Sulfate species, resulted from SO2 oxidation, played dual roles on catalytic activity. On aged samples, the slow decomposition of accumulated sulfate species on catalyst surface led to poor NO conversion due to the blockage of these species on active sites. On the other hand, catalytic activity was greatly enhanced in the low temperature region because of the enhanced intensity of Lewis acid site caused by the adsorbed sulfate species. The rate of sulfate accumulation on the Ag/TiO2–Al2O3 system was relatively slow. As a consequence, the system showed superior capability for selective adsorption of NO and SO2 toleration to the Ag/Al2O3 catalyst.  相似文献   

6.
以Al_2O_3为载体,RuCl_3·xH_2O和FeCl_3·6H_2O为活性组分前驱体,采用吸附-沉淀法制备了Ru-Fe/Al_2O_3和Ru/Al_2O_3催化剂,以马来酸二甲酯加氢合成丁二酸二甲酯为探针反应,结合H_2-TPR和XRD表征技术,考察Fe改性Ru基催化剂的氧化-还原性能及催化活性。经氧化-还原循环处理后,催化剂Ru-Fe/Al_2O_3上马来酸二甲酯加氢活性高于Ru/Al_2O_3。XRD结果显示,经处理的Ru-Fe/Al_2O_3上未见金属Ru的特征衍射峰,而Ru/Al_2O_3上出现了金属Ru的特征衍射峰。结合H_2-TPR结果推断,Ru与Fe之间发生了相互作用,这种协同作用可以改善Ru/Al_2O_3催化剂的热稳定性。  相似文献   

7.
Selective catalytic reduction of NOx by C3H6 in the presence of H2 over Ag/Al2O3 was investigated using in situ DRIFTS and GC–MS measurements. The addition of H2 promoted the partial oxidation of C3H6 to enolic species, the formation of –NCO and the reactions of enolic species and –NCO with NOx on Ag/Al2O3 surface at low temperatures. Based on the results, we proposed reaction mechanism to explain the promotional effect of H2 on the SCR of NOx by C3H6 over Ag/Al2O3 catalyst.  相似文献   

8.
The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al2O3 with a bulk oxide has been investigated. The oxides studied were: Co3O4, Mn2O3, Cr2O3, CuO, Fe2O3, NiO, CeO2, SnO2, ZnO and V2O5. Under lean C3H6-SCR conditions, these oxides (with the exception of SnO2) convert selectively NO to NO2. When mechanically mixed with Au/Al2O3, the Mn2O3 and Co3O4 oxides and, to a much greater extent, CeO2 act synergistically with this catalyst greatly enhancing its SCR performance. It was found that their synergistic action is not straightforwardly related to their activity for NO oxidation to NO2. The exhibited catalytic synergy may be due to the operation of either remote control or a bifunctional mechanism. In the later case, the key intermediate must be a short-lived compound and not the NO2 molecule in gas-phase.  相似文献   

9.
The effectiveness of Ag/Al2O3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al2O3, and Al(OH)3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O2, NO + O2-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C3H6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C3H6 conversion was achieved over Ag/Al2O3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al2O3 (I) is deemed to be crucial for NO selective reduction into N2. By contrast, a high C3H6 conversion simultaneously with a moderate N2 yield was observed over Ag/Al2O3 (II) prepared from a γ-Al2O3 source. The larger particles of AgmO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al2O3 (III) was obtained via employing a Al(OH)3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al2O3 (I). A subsequent calcination of Ag/Al2O3 (III) at 800 °C led to the generation of Ag/Al2O3 (IV) catalyst yielding a significant enhancement in both N2 yield and C3H6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al2O3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al2O3 (II and V) > Ag/Al2O3 (IV) > Ag/Al2O3 (I) > Ag/Al2O3 (III) and Al2O3 (I). The formation of nitrate species is an important step for the deNOx process, which can be promoted by increasing O2 feed concentration as evidenced by NO + O2-TPD study for Ag/Al2O3 (I), achieving a better catalytic performance.  相似文献   

10.
The phase diagram of the Al2O3–ZrO2–Nd2O3 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 Nd2O3·11Al2O3 + F-ZrO2 + NdAlO3. 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 Al2O3–ZrO2–Nd2O3 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   

11.
Nanosized particles dispersed uniformly on Al2O3 particles were prepared from the decomposition of precursor Cr(CO)6 by metal organic chemical vapor deposition (MOCVD) in a fluidized chamber. These nanosized particles consisted of Cr2O3, CrC1−x, and C. A solid solution of Al2O3–Cr2O3 and an Al2O3–Cr2O3/Cr3C2 nanocomposite were formed when these fluidized powders were pre-sintered at 1000 and 1150 °C before hot-pressing at 1400 °C, respectively. In addition, an Al2O3–Cr2O3/Cr-carbide (Cr3C2 and Cr7C3) nanocomposite was formed when the particles were directly hot pressed at 1400 °C. The interface between Cr3C2 and Al2O3 is non-coherent, while the interface between Cr7C3 and Al2O3 is semi-coherent.  相似文献   

12.
Catalytic performance of Sn/Al2O3 catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NOx by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO2 had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al2O3 (SG) catalyst, and the maximum NO2 conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NOx desorption accompanied with O2 around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H2O and SO2 at low temperature, and the temperature window was also broadened in the presence of H2O and SO2, however the NOx desorption and NO conversion decreased sharply on the 300 ppm SO2 treated catalyst, the catalytic activity was inhibited by the presence of SO2 due to formation of sulfate species (SO42−) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al2O3 (SG) was not decreased in the presence of large oxygen.  相似文献   

13.
Both low loaded 15% Co/Al2O3 and more highly loaded 25% Co/Al2O3 catalysts are studied, in order to explore the impact of cluster size on the stability of the cobalt cluster to support-influenced reoxidation processes at high H2O/CO ratios. XAFS and activity data suggest that there are two regions for the water effect: at lower H2O/CO ratios water influences CO conversion by reversible kinetic effects while at higher H2O/CO ratios cobalt re-oxidation processes occur. The latter regime where water was added at and above 25% are examined. Synthesis conditions were maintained constant while argon balancing gas was replaced by added water. Catalyst samples were withdrawn from the reactor during synthesis at different partial pressures of added water and cooled in the wax product under inert gas. The EXAFS results suggest that, unlike the smaller clusters on unpromoted and, especially noble-metal promoted, 15% Co/Al2O3 catalysts, the larger crystallites (>10 nm by chemisorption and XRD) on 25% Co/Al2O3 undergo oxidation by H2O to CoO, most likely confined to the surface. The clusters are re-reduced when H2O was switched off, and the activity displayed an important recovery.  相似文献   

14.
The role of La2O3 loading in Pd/Al2O3-La2O3 prepared by sol–gel on the catalytic properties in the NO reduction with H2 was studied. The catalysts were characterized by N2 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   


15.
Catalytic activities of Al2O3–TiO2 supporting CoMo and NiMo sulfides (CoMoS and NiMoS) catalysts were examined in the transalkylation of isopropylbenzene and hydrogenation of naphthalene as well as the hydrodesulfurization (HDS) of model sulfur compounds, conventional gas oil (GO), and light cycle oil (LCO). Al2O3–TiO2 supporting catalysts exhibited higher activities for these reactions except for the HDS of the gas oil than a reference Al2O3 supporting catalyst, indicating the correlation of these activities. Generally, more content of TiO2 promoted the activities. Inferior activity of the catalyst for HDS of the gas oil is ascribed to its inferior activity for HDS of dibenzothiophene (DBT) in gas oil as well as in model solvent decane, while the refractory 4,6-dimethyldibenzothiophene (4,6-DMDBT) in gas oil as well as in decane was more desulfurized on the catalyst. Characteristic features of Al2O3–TiO2 catalyst are discussed based on the paper results.  相似文献   

16.
A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 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 H2O and CO2 on NOx storage. The Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is primarily trapped on Al2O3 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 NOx/m2, 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/Al2O3 catalyst are coordinated on the Al2O3 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   


17.
A series of La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O2, NO + O2, C3H6, in the absence or presence of 5% H2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C3H6, 1% O2, 0 or 10% H2O, and 50,000 h−1 space velocity. The objective was to investigate the influence of H2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N2 yield, and 90% C3H6 conversion) was achieved at 600 °C over LaFe0.8Cu0.2O3 under a dry feed stream. With the exposure of LaFe0.8Cu0.2O3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N2 yield, and 86% C3H6 conversion. A competitive adsorption between H2O vapor with O2 and NO molecules at anion vacancies over LaFe0.8Cu0.2O3 was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C3H6 + NO + O2 reaction. This H2O deactivation was also verified to be strictly reversible by removing steam from the feed.  相似文献   

18.
The effect of oxygen concentration on the pulse and steady-state selective catalytic reduction (SCR) of NO with C3H6 over CuO/γ-Al2O3 has been studied by infrared spectroscopy (IR) coupled with mass spectroscopy studies. IR studies revealed that the pulse SCR occurred via (i) the oxidation of Cu0/Cu+ to Cu2+ by NO and O2, (ii) the co-adsorption of NO/NO2/O2 to produce Cu2+(NO3)2, and (iii) the reaction of Cu2+(NO3)2 with C3H6 to produce N2, CO2, and H2O. Increasing the O2/NO ratio from 25.0 to 83.4 promotes the formation of NO2 from gas phase oxidation of NO, resulting in a reactant mixture of NO/NO2/O2. This reactant mixture allows the formation of Cu2+(NO3)2 and its reaction with the C3H6 to occur at a higher rate with a higher selectivity toward N2 than the low O2/NO flow. Both the high and low O2/NO steady-state SCR reactions follow the same pathway, proceeding via adsorbed C3H7---NO2, C3H7---ONO, CH3COO, Cu0---CN, and Cu+---NCO intermediates toward N2, CO2, and H2O products. High O2 concentration in the high O2/NO SCR accelerates both the formation and destruction of adsorbates, resulting in their intensities similar to the low O2/NO SCR at 523–698 K. High O2 concentration in the reactant mixture resulted in a higher rate of destruction of the intermediates than low O2 concentration at temperatures above 723 K.  相似文献   

19.
In situ growth of needlelike LaAl11O18 grains reinforcing Al2O3 composites can be fabricated by a coprecipitation method using La(NO3)3√6H2O and Al(NO3)3√9H2O as starting materials. The new two-step process involved firstly preparing needlelike LaAl11O18 grains distributed homogeneously in Al2O3 powder and then pressureless sintering the composite powders. The Al2O3/25 vol.%LaAl11O18 samples pressureless sintered at 1550°C for 4 h achieve relative density up to 96.5% and exhibit a bending strength of 420±30 MPa and a fracture toughness of 4.3±0.4 MPa m1/2.  相似文献   

20.
A mean field model, for storage and desorption of NOx in a Pt/BaO/Al2O3 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/Al2O3; (ii) NO oxidation on Pt/BaO/Al2O3; (iii) NOx storage on BaO/Al2O3; (iv) NOx storage on Pt/BaO/Al2O3 with thermal regeneration and (v) NOx storage on Pt/BaO/Al2O3 with regeneration using C3H6. In this paper, we focus on the last sub-system. The kinetic model for NOx storage on Pt/BaO/Al2O3 was constructed with kinetic parameters obtained from the NO oxidation model together with a NOx storage model on BaO/Al2O3. This model was not sufficient to describe the NOx storage experiments for the Pt/BaO/Al2O3, because the NOx desorption in TPD experiments was larger for Pt/BaO/Al2O3, compared to BaO/Al2O3. 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 NOx from Pt/BaO/Al2O3. To this NOx storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO2 and C3H6. The main reactions for continuous reduction of NOx 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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