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1.
A catalytic deSoot–deNO x system, comprising Pt and Ce fuel additives, a Pt-impregnated wall-flow monolith soot filter and a vanadia-type monolithic NH 3-SCR catalyst, was tested with a two-cylinder DI diesel engine. The soot removal efficiency of the filter was 98–99 mass% with a balance temperature (stationary pressure drop) of 315 °C at an engine load of 55%. The NO x conversion ranged from 40 to 73%, at a NH 3/NO x molar ratio of 0.9. Both systems were measured at a GHSV of 52 000 l/(l h). The maximum NO x conversion was obtained at 400 °C. The reason for the moderate deNO x performance is discussed. No deactivation was observed after 380 h time on stream. The NO x emission at high engine loads is around 15% lower than that of engines running without fuel additives. 相似文献
2.
The selective catalytic reduction (SCR) of NO x assisted by propene is investigated on Pd/Ce 0.68Zr 0.32O 2 catalysts (Pd/CZ), and is compared, under identical experimental conditions, with that found on a Pd/SiO 2 reference catalyst. Physico-chemical characterisation of the studied catalysts along with their catalytic properties indicate that Pd is not fully reduced to metallic Pd for the Pd/CZ catalysts. This study shows that the incorporation of Pd to CZ greatly promotes the reduction of NO in the presence of C 3H 6. These catalysts display very stable deNO x activity even in the presence of 1.7% water, the addition of which induces a reversible deactivation of about 10%. The much higher N 2 selectivity obtained on Pd/CZ suggests that the lean deNO x mechanism occurring on these catalysts is different from that occurring on Pd 0/SiO 2. A detailed mechanism is proposed for which CZ achieves both NO oxidation to NO 2 and NO decomposition to N 2, whereas PdO x activates C 3H 6 via ad-NO 2 species, intermediately producing R-NO x compounds that further decompose to NO and C xH yO z. The role of the latter oxygenates is to reduce CZ to provide the catalytic sites responsible for NO decomposition. The proposed C 3H 6-assisted NO decomposition mechanism stresses the key role of NO 2, R-NO x and C xH yO z as intermediates of the SCR of NO x by hydrocarbons. 相似文献
3.
Pt-USY was used for the selective catalytic reduction of NO x with hydrocarbons in the presence of excess oxygen. The catalyst was prepared by an ion-exchange method and characterized by XRD, TEM, CO chemisorption, and Ar adsorption at 87 K. The platinum particle size distribution was found to be broad (2–20 nm), with no apparent sintering of the active phase during the HC-SCR process after 25 h time-on-stream. Generally, large metal clusters (>15 nm) are situated at the external surface of the zeolite, while the smaller ones are located in the pores of the support. Pt-USY shows an excellent activity in the deNO x reaction (molar NO x conversion 90% at 475 K) with propene as the reductant in 5 kPa O 2, as well as stable operation during time-on-stream. Propane only yields a low NO x conversion compared to propene. The presence of high oxygen contents (5–10 kPa O 2) slightly inhibits the reaction. No significant decrease in deNO x activity was observed at high space velocities (up to 100,000 h −1). The presence of SO 2 and H 2O in the feed stream did not significantly affect the deNO x activity. Pt-USY performs better under lean-burn conditions than other Pt-catalysts supported on e.g. ZSM-5, Al 2O 3, or SiO 2. The selectivity to N 2 was similar to the other Pt-based catalysts (30%), the other major product being N 2O. 相似文献
4.
SCR-deNO x reaction and SO 2–SO 3 oxidation tests were carried out by different research groups over fresh and used EUROCAT oxide samples in order to characterize the reactivity of the catalysts and to compare data obtained in several laboratories (Politecnico of Milan, Università of Salerno, ENEL of Milan, Boreskov Insitute of Catalysis). Data are presented which indicate that the used EUROCAT catalyst is slightly more active both in the deNOx reaction and SO2–SO3 oxidation than the fresh sample. An analyses of data collected over honeycomb catalysts by means of a 2D, single-channel model of the SCR monolith reactor has been performed to evaluate the intrinsic kinetic constant of the deNOx reaction; a satisfactory comparison has been obtained between estimation of the intrinsic kinetic constant and estimation of the intrinsic catalyst activity from data collected over powdered catalysts. A good agreement has been found in the experimental results collected in the different labs, both for the deNOx reaction and SO2–SO3 oxidation. 相似文献
5.
Samples of ash collected from a full-scale utility boiler cofiring 80% wood waste with 20% Powder River Basin (PRB) coal were mixed with ground selective catalytic reduction (SCR) catalyst and exposed to simulated flue gas. Changes in mass were recorded with time, and mass gains were found to be highest without SCR catalyst present. Ash samples were analyzed before and after testing to determine what mechanisms had led to mass gain. The ash had reacted with gas-phase SO 2 to form solid sulfates. Mass gain by sulfation would likely cause ash particles to grow and cover catalyst pores in the field, leading to catalyst deactivation and reduced NO x control. 相似文献
6.
The Co/MFI(SiO 2/Al 2O 3 = 30) were prepared by a precipitation method with NaOCl in alkali solutions exhibited high activities to N 2 at 250 °C for the selective catalytic reduction (SCR) of NO x. These catalysts showed two UV–vis bands at 700 and 400 nm, indicating the presence of octahedral Co(III) as well as tetrahedral Co(II). The high SCR activity over such Co(III, II)/MFI(30) seems to come from Co(III)---O moieties. The Co(II)MFI(30) catalysts prepared from Co(II)Cl 2 exhibited low SCR activities due to the presence of tetrahedral Co(II) ions in MFI. Less CO formation occurred over Co/MFI catalysts. The Fe/MFI(30) catalyst exhibited high activity due to the presence of some Fe---O species in MFI but more amount of CO were produced during SCR. H/MFI(30) catalyst exhibited a good SCR activity. However, more amount of carbonaceous deposits were produced on it. The correlation between acid concentration and SCR activity was discussed over H/MFIs. 相似文献
7.
The deactivation of a commercial type V 2O 5-WO 3-TiO 2 monolith catalyst under biomass combustion was studied at a full-scale grate-fired power plant burning straw/wood using a slip stream pilot scale reactor. The aerosols in the flue gas consisted of a mixture of potassium chloride and sulphate. Three catalyst elements were exposed at 350 °C, and one element was exposed at 250 °C for comparison. The catalyst activity was measured in the reactor at the exposure temperature by addition of NH 3 and extra NO. The activity, in terms of a first-order rate constant, dropped by 52% after about 1140 h indicating a very fast deactivation compared to coal firing. It was also found that the reactor temperature was not of importance for the deactivation rate. SEM-EDX analysis showed that particle deposition and pore blocking contributed to the deactivation by decreasing the diffusion rate of NO and NH 3 into the catalyst. However, potassium also penetrated into the catalyst wall and the resulting average K/V ratio in the catalyst structure was high enough (about 0.3–0.5) for a significant chemical deactivation. Chemisorption studies carried out in situ showed that the amount of chemisorbed NH 3 on the catalyst decreased as a function of exposure time, which reveals that Brøndsted acid sites had reacted with potassium compounds and thereby rendered inactive. When washed by 0.5 M H 2SO 4 the regenerated catalyst regains a higher activity than that of the fresh catalyst at temperatures higher than 300 °C, but even though reactivation is possible, the deactivation rate appears too high for practical use of the SCR process in straw combustion. 相似文献
8.
Operating the SCR DeNO x reactor at temperatures below 200 °C results in a considerable saving in operating costs. Plant experience shows that on the catalysts in these second generation DeNO x plants, even for flue gases with SO 2 concentration below 10 mg/m 3, over 1–2 years operating time sizeable quantities of ammonium sulfates accumulate. Ammonium sulfates deposited on V 2O 5–WO 3/TiO 2 catalysts react with NO x to nitrogen and sulfuric acid. Second-order rate constants of this reaction for temperatures of 170 °C have been derived. It could be shown that the sulfuric acid formed on the catalyst is displaced by water vapour and desorbs resulting in gas phase concentrations of up to 6.5 mg acid/m 3 flue gas. Plant equipment downstream of the ammonium sulfate containing low temperature DeNO x catalysts has to be protected against the corrosive action of the sulfuric acid in the flue gases leaving the DeNO x reactor. 相似文献
9.
The surface structure analysis of a model catalyst MoO x/TiO 2(110) was for the first time performed by polarization-dependent total-reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) in three different directions of the crystal surface. Two samples of MoO x/TiO 2(110) were prepared by an impregnation of (NH 4) 6Mo 7O 24·4H 2O using ultra high purity water and normal distilled water. The PTRF-XAFS analysis revealed that anisotropic Mo dimer species was preferentially formed on the TiO 2(110) surface, with Mo–Mo bond (0.335 nm) parallel to the
direction when the ultra high purity water was used as the solvent. On the other hand, the Mo oxide on the surface prepared using normal distilled water had a symmetric tetrahedral structure (MoO 4) with Mo–O of 0.176 nm, which was due to the coexistence of alkaline metals at the surface. 相似文献
10.
A novel activated carbon-supported vanadium oxide catalyst was studied for SCR of NO with NH 3 at low temperatures (100 – 250°C). The effects of reaction temperature, preparation conditions and SO 2 on SCR activity were evaluated. The results show that this catalyst has a high catalytic activity for NO–NH 3–O 2 reaction at low temperatures. Preoxidation of the calcined catalyst helps improve catalytic activity. V 2O 5 loading, other than calcination temperature, gives a significant influence on the activity. SO 2 in the flue gas does not de-activate the catalyst but improves it. A stability test of more than 260 h shows that the catalyst is highly active and stable in the presence of SO 2. 相似文献
11.
The fast SCR reaction using equimolar amounts of NO and NO 2 is a powerful means to enhance the NO x conversion over a given SCR catalyst. NO 2 fractions in excess of 50% of total NO x should be avoided because the reaction with NO 2 only is slower than the standard SCR reaction. At temperatures below 200 °C, due to its negative temperature coefficient, the ammonium nitrate reaction gets increasingly important. Half of each NH3 and NO2 react to form dinitrogen and water in analogy to a typical SCR reaction. The other half of NH3 and NO2 form ammonium nitrate in close analogy to a NOx storage-reduction catalyst. Ammonium nitrate tends to deposit in solid or liquid form in the pores of the catalyst and this will lead to its temporary deactivation. The various reactions have been studied experimentally in the temperature range 150–450 °C for various NO2/NOx ratios. The fate of the deposited ammonium nitrate during a later reheating of the catalyst has also been investigated. In the absence of NO, the thermal decomposition yields mainly ammonia and nitric acid. If NO is present, its reaction with nitric acid on the catalyst will cause the formation of NO2. 相似文献
12.
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
13.
燃煤烟气中有机污染物的排放逐渐引起重视。锰铈(MnCe)基催化剂被认为是一种低温高效、低成本的可应用于燃煤烟气污染物脱除的催化剂。本文通过浸渍法制备了MnCe基催化剂,通过物理化学表征和烟气模拟台架实验,研究了MnCe基催化剂配比、反应工况、烟气复杂组分(H 2O、SO 2、NH 3、NO)以及典型污染物脱除过程(Hg 0和NO催化转化)对催化脱除烟气中邻二甲苯行为的影响和规律。实验结果表明,Mn和Ce摩尔比为6∶4时催化剂脱除邻二甲苯效率良好。反应空速和MnCe负载量在低温下对催化脱除效率影响显著。烟气中H 2O、SO 2、NH 3、NO等组分对催化产生抑制作用,但抑制程度与作用机理具有显著差异。MnCe基催化剂对烟气SCR脱硝与Hg 0催化氧化皆具有较高效率,且受烟气中邻二甲苯影响较小;但受SCR气氛与Hg 0抑制,邻二甲苯催化脱除反应效率明显降低。 相似文献
14.
The development of a catalytically active filter element for combined particle separation and NO x removal or VOC total oxidation, respectively, is presented. For NO x removal by selective catalytic reduction (SCR) a catalytic coating based on a TiO 2–V 2O 5–WO 3 catalyst system was developed on a ceramic filter element. Different TiO 2 sols of tailor-made mean particle size between 40 and 190 nm were prepared by the sol–gel process and used for the impregnation of filter element cylinders by the incipient wetness technique. The obtained TiO 2-impregnated sintered filter element cylinders exhibit BET surface areas in the range between 0.5 and 1.3 m 2/g. Selected TiO 2-impregnated filter element cylinders of high BET surface area were catalytically activated by impregnation with a V 2O 5 and WO 3 precursor solution. The obtained catalytic filter element cylinders show high SCR activity leading to 96% NO conversion at 300 °C, a filtration velocity of 2 cm/s and an NO inlet concentration of 500 vol.-ppm. The corresponding differential pressures fulfill the requirements for typical hot gas filtration applications. For VOC total oxidation, a TiO 2-impregnated filter element support was catalytically activated with a Pt/V 2O 5 system. Complete oxidation of propene with 100% selectivity to CO 2 was achieved at 300 °C, a filtration velocity of 2 cm/s and a propene inlet concentration of 300 vol.-ppm. 相似文献
15.
A comparison study was carried out on non-thermal plasma (NTP)-assisted selective catalytic reduction (SCR) of NO x by propene over Ag/USY and Ag/Al 2O 3 catalysts. Ag/USY was almost inactive in thermal SCR while it showed obvious activities in NTP-assisted SCR at 100 °C–200 °C. Although the NO x conversion over Ag/Al 2O 3 was also enhanced at 300 °C–400 °C by the assistance of NTP, it was ineffective below 250 °C. The intermediates over Ag/USY and Ag/Al 2O 3 were investigated using in situ DRIFTS method. It was found that key intermediates in HC-SCR, such as NCO, CN, oxygenates and some N-containing organic species were enriched after the assistance of NTP. The differences in the behaviors of above intermediates were not found between these two kinds of catalysts. However, some evidences suggested that different properties of the absorbed NO x species resulted in the distinction of SCR reactions over Ag/USY and Ag/Al 2O 3. TPD profiles of Ag/Al 2O 3 showed that nitrates formed over the catalyst were quite stable at low temperatures, which might occupy the active sites and were unfavorable to SCR reactions. The nitrates over Ag/USY were unstable, among which the unidentate nitrate species is probably contributed to the SCR reactions at low temperatures. 相似文献
16.
Combined effect of H 2O and SO 2 on V 2O 5/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH 3 at lower temperatures was studied. In the absence of SO 2, H 2O inhibits the catalytic activity, which may be attributed to competitive adsorption of H 2O and reactants (NO and/or NH 3). Although SO 2 promotes the SCR activity of the V 2O 5/AC catalyst in the absence of H 2O, it speeds the deactivation of the catalyst in the presence of H 2O. The dual effect of SO 2 is attributed to the SO 42− formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H 2O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H 2O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V 2O 5 loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h −1 and temperature of 250 °C. 相似文献
17.
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
18.
MnO x–CeO 2 mixed oxides with a Mn/(Mn + Ce) molar ratios of 0–1 were prepared by a modified coprecipitation method and investigated for the complete oxidation of formaldehyde. The MnO x–CeO 2 with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnO x–CeO 2 mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnO x–CeO 2 solid solution greatly improved the low-temperature reducibility, resulting in a higher catalytic activity for the oxidation of formaldehyde. Promoting effect of Pt on the MnO x–CeO 2 mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnO x–CeO 2 catalyst prepared from chlorine-free precursor showed extremely high activity and stability after pretreatment with hydrogen at 473 K. 100% conversion of formaldehyde was achieved at ambient temperature and no deactivation was observed for 120 h time-on-stream. The promoting effect of Pt was ascribed to enhance the effective activation of oxygen molecule on the MnO x–CeO 2 support. 相似文献
19.
A quaternary catalyst library of 56 samples comprising all combinations of four elements, viz. Ag, Co, Cu, In, with six equally spaced atomic fraction increments from 0 to 1 was prepared by impregnation of a proprietary mesoporous alumina support. Catalytic properties of the library were tested in the selective catalytic reduction (SCR) of NO x by propane under lean conditions in the temperature range 400–500 °C. The catalytic data acquired by a parallel 64-channel microreactor system with automated time-of-flight mass spectrometric analysis have been evaluated regarding selectivity–compositional relationships, synergistic effects for NO x conversion, and efficiency of propane utilization. Full conversion of NO x is achieved over Ag–Co combinations at 450 °C with N 2 selectivities of more than 90% and reductant utilization of 20% in a feed of 1500 ppm NO, 1500 ppm propane and 5 vol.% O 2 (space velocity of 36,000 cm 3 g cat−1 h −1). For the single-component catalysts Ag/Al 2O 3, Co/Al 2O 3, Cu/Al 2O 3, and In/Al 2O 3, the state of the elements on the mesoporous alumina was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Cobalt forms a spinel-like cobalt aluminate phase whereas copper and indium are present as oxides with small sizes not detectable by XRD. Silver occurs in both metallic state and as Ag 2O, and forms Ag n clusters of at least two different sizes, predominantly with diameters of about 30 nm. The conclusions are consistent with the reducibility of the single-component catalysts samples by H 2. Surface area measurements and pore size distributions revealed reasonable modifications of the textural properties. The main pore size of the alumina support is decreased from 7 to ca. 5 nm after loading of the active components. 相似文献
20.
The catalytic activities of ceria-zirconia mixed oxides Ce xZr 1−xO 2 ( x = 0.17, 0.42, 0.62 and 0.8) are determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that all supports are active in deNO x reaction in the presence of the previous hydrocarbons. However, their catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NO x consumption. This activity was correlated with physicochemical properties determined by a linear solvation energy relationship (LSER) approach. Moreover, a mechanism of HC assisted reduction of NO is proposed on ceria-zirconia supported catalysts. This mechanism is divided in three catalytic cycles involving: (i) the oxidation of NO into NO 2, (ii) the reaction of NO 2 and the hydrocarbons leading to RNO x species and C xH yO z, and finally (iii) the decomposition of NO assisted by these latter C xH yO z species. 相似文献
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