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1.
Effect of additives, In 2O 3, SnO 2, CoO, CuO and Ag, on the catalytic performance of Ga 2O 3–Al 2O 3 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 H 2O, CoO, CuO and Ag showed good additive effect. When H 2O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga 2O 3–Al 2O 3 was depressed considerably, while an intensifying effect of H 2O was observed for In 2O 3- and SnO 2-doped Ga 2O 3–Al 2O 3. Of several metal oxide additives, In 2O 3-doped Ga 2O 3–Al 2O 3 showed the highest activity for NO reduction by propene in the presence of H 2O. Kinetic studies on NO reduction over In 2O 3–Ga 2O 3–Al 2O 3 revealed that the rate-determining step in the absence of H 2O is the reaction of NO 2 formed on Ga 2O 3–Al 2O 3 with C 3H 6-derived species, whereas that in the presence of H 2O is the formation of C 3H 6-derived species. We presumed the reason for the promotional effect of H 2O as follows: the rate for the formation of C 3H 6-derived species in the presence of H 2O is sufficiently fast compared with that for the reaction of NO 2 with C 3H 6-derived species in the absence of H 2O. Although the retarding effect of SO 2 on the activity was observed for all of the catalysts, SnO 2–Ga 2O 3–Al 2O 3 showed still relatively high activity in the lower temperature region. 相似文献
2.
The selective catalytic reduction (SCR) of NO by C 3H 6 in excess oxygen was evaluated and compared over Ag/Al 2O 3 and Cu/Al 2O 3 catalysts. Ag/Al 2O 3 showed a high activity for NO reduction. However, Cu/Al 2O 3 showed a high activity for C 3H 6 oxidation. The partial oxidation of C 3H 6 gave surface enolic species and acetate species on the Ag/Al 2O 3, but only an acetate species was clearly observed on the Cu/Al 2O 3. The enolic species is a more active intermediate towards NO + O 2 to yield—NCO species than the acetate species on the Ag/Al 2O 3 catalyst. The Ag and Cu metal loadings and phase changes on Al 2O 3 support can affect the activity and selectivity of Ag/Al 2O 3 and Cu/Al 2O 3 catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al 2O 3 catalyst for NO reduction is higher than that of the Cu/Al 2O 3 catalyst. 相似文献
3.
A series of CoO x/Al 2O 3 catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C 3H 8. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co 3O 4 crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoO x/Al 2O 3 catalyst shows high activity in SCR of NO by C 3H 8 (100% conversion of NO at 723 K, GHSV: 10,000 h −1). The activity of the selective catalytic reduction of NO by C 3H 8 increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl 2O 4 crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co 3O 4 crystallites catalyze the combustion of C 3H 8 only. 相似文献
4.
The effectiveness of Ag/Al 2O 3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al 2O 3, 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, O 2, NO + O 2-temperature programmed desorption (TPD), H 2-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 C 3H 6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C 3H 6 conversion was achieved over Ag/Al 2O 3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al 2O 3 (I) is deemed to be crucial for NO selective reduction into N 2. By contrast, a high C 3H 6 conversion simultaneously with a moderate N 2 yield was observed over Ag/Al 2O 3 (II) prepared from a γ-Al 2O 3 source. The larger particles of Ag mO ( m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al 2O 3 (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 Al 2O 3 (I). A subsequent calcination of Ag/Al 2O 3 (III) at 800 °C led to the generation of Ag/Al 2O 3 (IV) catalyst yielding a significant enhancement in both N 2 yield and C 3H 6 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/Al 2O 3 (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/Al 2O 3 (II and V) > Ag/Al 2O 3 (IV) > Ag/Al 2O 3 (I) > Ag/Al 2O 3 (III) and Al 2O 3 (I). The formation of nitrate species is an important step for the deNO x process, which can be promoted by increasing O 2 feed concentration as evidenced by NO + O 2-TPD study for Ag/Al 2O 3 (I), achieving a better catalytic performance. 相似文献
5.
Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO 2-doped Ga 2O 3–Al 2O 3 prepared by sol–gel method. Although SnO 2-doped Ga 2O 3–Al 2O 3 gave lower NO conversion than Ga 2O 3–Al 2O 3 in the absence of H 2O, the activity was enhanced considerably by the presence of H 2O and much higher than that of Ga 2O 3–Al 2O 3. The presence of SnO 2 and Ga 2O 3–Al 2O 3 species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H 2O. The promotional effect of H 2O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H 2O. The other is the selective inhibition by H 2O of the reaction steps resulting in propene oxidation to CO x without reducing NO. 相似文献
6.
An In 2O 3/Al 2O 3 catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO 2 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 NO X adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO 2, and the amount of ad-NO 3− species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO 2 enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO 2 at low temperature, because active C 3H 6 (partially oxidized C 3H 6) is crucial at low temperature. 相似文献
7.
The activity and selectivity of rhenium promoted cobalt Fischer–Tropsch catalysts supported on Al 2O 3, TiO 2 and SiO 2 have been studied in a fixed-bed reactor at 483 K and 20 bar. Exposure of the catalysts to water added to the feed deactivates the Al 2O 3 supported catalyst, while the activity of the TiO 2 and SiO 2 supported catalysts increased. However, at high concentrations of water both the SiO 2 and TiO 2 supported catalyst deactivated. Common for all catalysts was an increase in C 5+ selectivity and a decrease in the CH 4 selectivity by increasing the water partial pressure. The catalysts have been characterized by scanning transmission electron microscope (STEM), BET, H 2 chemisorption and X-ray diffraction (XRD). 相似文献
8.
The nature of the silver phases of Ag/Al 2O 3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV–VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO 2. The UV–VIS spectrum of the 1.2 wt.% Ag/Al 2O 3 exhibited essentially one band associated with Ag + species and the NO 2 yields measured over this material were negligible. A 10 wt.% Ag/Al 2O 3 material showed the presence of oxidic species of silver (as isolated Ag + cations and silver aluminate), but the UV–VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO 2 of this sample was moderate. The same 10% sample either reduced in H 2 or used for the C 3H 6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO 2. These data show that the structure and nature of the silver phases of Ag/Al 2O 3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O 2). The low activity for N 2 formation during the C 3H 6-SCR of NO (reported in an earlier study) over the high loading sample can, therefore, be related to the presence of metallic silver, which is yet a good catalyst for NO oxidation to NO 2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO 2. 相似文献
9.
The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al 2O 3 catalysts on the surface properties and reactivity for NO reduction by C 3H 6 in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al 2O 3 catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al 2O 3 and 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalysts calcined at 1073 K possess a CuAl 2O 4 phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C 3H 6 shows that the CuAl 2O 4 is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K, although these catalysts possess the same CuAl 2O 4 phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K is attributed to the formation of less active CuAl 2O 4 phase with high aggregation and preferential promotion of C 3H 6 combustion to CO x by MnO 2. The engine dynamometer test for NO reduction shows that the C 3H 6 is a more effective reducing agent for NO reduction than the C 2H 5OH. The maximum reactivity for NO reduction by C 3H 6 is reached when the NO/C 3H 6 ratio is one. 相似文献
10.
NO reduction to N 2 by C 3H 6 was investigated and compared over Cu-Al 2O 3 catalysts prepared by four different methods, namely, the conventional impregnation, co-precipitation, evaporation of a mixed aqueous solution, and xerogel methods. It was found that the catalyst preparation method as well as the Cu content exerts a significant influence on catalyst activity. For the catalysts prepared by the first three preparation methods, with the increase of Cu content from 5 to 15 wt%, the maximum NO reduction conversion decreased slightly, but the temperature for the maximum NO reduction also decreased. For the xerogel Cu-Al 2O 3, there was a significant decrease in NO reduction conversion with the increase of Cu content from 5 to 10 wt%. In the absence of water vapour, the Cu-Al 2O 3 catalyst prepared by the impregnation method exhibited the highest activity toward NO reduction. The purity of alumina support was found to be a crucial factor to the activity of the Cu-Al 2O 3 catalyst prepared by impregnation. In the presence of water vapour, a substantial decrease in NO conversion was observed for the Cu-Al 2O 3 catalysts prepared by the first three methods, especially for the impregnated Cu-Al 2O 3 catalyst. In contrast, the presence of water vapour showed only a minor influence on the xerogel 5 wt% Cu-Al 2O 3 and it showed the highest activity for NO reduction in the presence of 20% water vapour. The xerogel 5 wt% Cu-Al 2O 3 catalyst was also found to be less affected by a 5 wt% sulfate deposition than the Cu-Al 2O 3 catalysts prepared by other methods. 相似文献
11.
The effects of carbon dioxide on the dehydrogenation of C 3H 8 to produce C 3H 6 were investigated over several Cr 2O 3 catalysts supported on Al 2O 3, active carbon and SiO 2. Carbon dioxide exerted promoting effects only on SiO 2-supported Cr 2O 3 catalysts. The promoting effects of carbon dioxide over a Cr 2O 3/SiO 2 catalyst were to enhance the yield of C 3H 6 and to suppress the catalyst deactivation. 相似文献
12.
In this study, Pd/Al 2O 3 and Pd/BaO/Al 2O 3 metallic monoliths were used to investigate the effect of BaO in C 2H 4 and CO oxidation as well as in NO reduction. A FT-IR gas analyser was used to study the activity of the catalysts. Several activity experiments carried out with dissimilar feedstreams revealed that BaO enhances CO and C 2H 4 oxidation as well as NO reduction reactions in rich conditions. This effect is due to BaO, which causes a decrease in the ethene poisoning of palladium. In lean conditions BaO is present in the form of Ba(OH) 2 which reacts with oxidised NO releasing water. Therefore, NO was stored during the lean reaction. 相似文献
13.
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
14.
The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al 2O 3 with a bulk oxide has been investigated. The oxides studied were: Co 3O 4, Mn 2O 3, Cr 2O 3, CuO, Fe 2O 3, NiO, CeO 2, SnO 2, ZnO and V 2O 5. Under lean C 3H 6-SCR conditions, these oxides (with the exception of SnO 2) convert selectively NO to NO 2. When mechanically mixed with Au/Al 2O 3, the Mn 2O 3 and Co 3O 4 oxides and, to a much greater extent, CeO 2 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 NO 2. 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 NO 2 molecule in gas-phase. 相似文献
15.
More than 0.22 mmol of isolated VO 4 species of V 2O 5/Al 2O 3 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.% V 2O 5/Al 2O 3, respectively, where the K/A ratio was 6.2. In addition, V 2O 5/Al 2O 3 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
16.
The performance of unpromoted and MO x-(M: alkali (earth), transition metal and cerium) promoted Au/Al 2O 3 catalysts have been studied for combustion of the saturated hydrocarbons methane and propane. As expected, higher temperatures are required to oxidize CH 4 (above 400 °C), compared with C 3H 8 (above 250 °C). The addition of various MO x to Au/Al 2O 3 improves the catalytic activity in both methane and propane oxidation. For methane oxidation, the most efficient promoters to enhance the catalytic performance of Au/Al 2O 3 are FeO x and MnO x. For C 3H 8 oxidation a direct relationship is found between the catalytic performance and the average size of the gold particles in the presence of alkali (earth) metal oxides. The effect of the gold particle size becomes less important for additives of the type of transition metal oxides and ceria. The results suggest that the role of the alkali (earth) metal oxides is related to the stabilization of the gold nanoparticles, whereas transition metal oxide and ceria additives may be involved in oxygen activation. 相似文献
17.
The adsorption of HCN on, its catalytic oxidation with 6% O 2 over 0.5% Pt/Al 2O 3, and the subsequent oxidation of strongly bound chemisorbed species upon heating were investigated. The observed N-containing products were N 2O, NO and NO 2, and some residual adsorbed N-containing species were oxidized to NO and NO 2 during subsequent temperature programmed oxidation. Because N-atom balance could not be obtained after accounting for the quantities of each of these product species, we propose that N 2 and was formed. Both the HCN conversion and the selectivity towards different N-containing products depend strongly on the reaction temperature and the composition of the reactant gas mixture. In particular, total HCN conversion reaches 95% above 250 °C. Furthermore, the temperature of maximum HCN conversion to N 2O is located between 200 and 250 °C, while raising the reaction temperature increases the proportion of NO x in the products. The co-feeding of H 2O and C 3H 6 had little, if any effect on the total HCN conversion, but C 3H 6 addition did increase the conversion to NO and decrease the conversion to NO 2, perhaps due to the competing presence of adsorbed fragments of reductive C 3H 6. Evidence is also presented that introduction of NO and NO 2 into the reactant gas mixture resulted in additional reaction pathways between these NO x species and HCN that provide for lean-NO x reduction coincident with HCN oxidation. 相似文献
18.
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
19.
Oxidation of propene and propane to CO 2 and H 2O has been studied over Au/Al 2O 3 and two different Au/CuO/Al 2O 3 (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co 3O 4/Al 2O 3 (4.1 wt.% Au) and Pt/Al 2O 3 (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO). A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al2O3 is almost as active as Pt/Al2O3, whereas Au/Co3O4/Al2O3 performs less than any of the CuO-containing gold-based catalysts. The light-off temperature for C3H8 oxidation is significantly higher than for C3H6. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al2O3 (gold particles less than 3 nm) and 4Au/Co3O4/Al2O3 (gold particles less than 5 nm). 相似文献
20.
A series of La(Co, Mn, Fe) 1−x(Cu, Pd) xO 3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N 2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O 2, NO + O 2, C 3H 6, in the absence or presence of 5% H 2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C 3H 6, 1% O 2, 0 or 10% H 2O, and 50,000 h −1 space velocity. The objective was to investigate the influence of H 2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N 2 yield, and 90% C 3H 6 conversion) was achieved at 600 °C over LaFe 0.8Cu 0.2O 3 under a dry feed stream. With the exposure of LaFe 0.8Cu 0.2O 3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N 2 yield, and 86% C 3H 6 conversion. A competitive adsorption between H 2O vapor with O 2 and NO molecules at anion vacancies over LaFe 0.8Cu 0.2O 3 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 C 3H 6 + NO + O 2 reaction. This H 2O deactivation was also verified to be strictly reversible by removing steam from the feed. 相似文献
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