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1.
The kinetics of the selective catalytic reduction (SCR) of NO by NH3 in the presence of O2 has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<TR<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O2, and essentially 0 with respect to NH3. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH3 was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) CuI is oxidized by O2 to “CuII-oxo”, (ii) “CuII-oxo” reacts with NO to yield “CuII-NxOy”, and (iii) finally “CuII-NxOy” is reduced by NH3 to give N2, H2O, and the regeneration of CuI (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that CuI or “CuII-oxo” species constitute the rate-determining active center.  相似文献   

2.
A novel activated carbon-supported vanadium oxide catalyst was studied for SCR of NO with NH3 at low temperatures (100 – 250°C). The effects of reaction temperature, preparation conditions and SO2 on SCR activity were evaluated. The results show that this catalyst has a high catalytic activity for NO–NH3–O2 reaction at low temperatures. Preoxidation of the calcined catalyst helps improve catalytic activity. V2O5 loading, other than calcination temperature, gives a significant influence on the activity. SO2 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 SO2.  相似文献   

3.
The unsteady-state kinetics of the selective catalytic reduction (SCR) of NO with NH3 is studied over V2O5–WO3/TiO2 model catalysts by means of the transient response method. NH3 strongly adsorbs onto the catalyst surface whereas NO does not adsorb appreciably. A dynamic mathematical model based on a Temkin-type desorption process for NH3 and a SCR reaction rate with a complex dependence on the ammonia surface coverage is well suited to represent the data.  相似文献   

4.
In situ Raman spectroscopy was used for studying the ternary 2% CrO3–6% V2O5/TiO2 catalyst, for which a synergistic effect between vanadia and chromia leads to enhanced catalytic performance for the selective catalytic reduction (SCR) of NO with NH3. The structural properties of this catalyst were studied under NH3/NO/O2/N2/SO2/H2O atmospheres at temperatures up to 400 °C and major structural interactions between the surface chromia and vanadia species are observed. The effects of oxygen, ammonia, water vapor and sulfur dioxide presence on the in situ Raman spectra are presented and discussed.  相似文献   

5.
In the off-gases of internal combustion engines running with oxygen excess, non-thermal plasmas (NTPs) have an oxidative potential, which results in an effective conversion of NO to NO2. In combination with appropriate catalysts and ammonia (NH3-SCR) or hydrocarbons (HC-SCR) as a reducing agent, this can be utilized to reduce nitric oxides (NO and NO2) synergistically to molecular nitrogen.

The combination of SCR and cold plasma enhanced the overall reaction rate and allowed an effective removal of NOX at low temperatures. Using NH3 as a reducing agent, NOX was converted to N2 on zeolites or NH3-SCR catalysts like V2O5–WO3/TiO2 at temperatures as low as 100–200 °C. Significant synergetic effects of plasma and catalyst treatment were observed both for NH3 stored by ion exchange on the zeolite and for continuous NH3 supply.

Certain modifications of Al2O3 and ZrO2 have been found to be effective as catalysts in the plasma-assisted HC-SCR in oxygen excess. With an energy supply of about 30 eV/NO-molecule, 500 ppm NO was reduced by more than half at a temperature of 300 °C and a space velocity of 20 000 h−1 at the catalyst. The synergistic combinations of NTP and both NH3- and HC-SCR have been verified under real diesel engine exhaust conditions.  相似文献   


6.
A new proton-conductive composite of NH4PO3–(NH4)2Mn(PO3)4 was synthesized and characterized as a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C. Thermal gravimetric analysis and X-ray diffraction investigation showed that (NH4)2Mn(PO3)4 was stable as a supporting matrix for NH4PO3. The composite conductivity, measured using impedance spectroscopy, improved with increasing the molar ratio of NH4PO3 in both dry and wet atmospheres. A conductivity of 7 mS cm−1 was obtained at 250 °C in wet hydrogen. Electromotive forces measured by hydrogen concentration cells showed that the composite was nearly a pure protonic conductor with hydrogen partial pressure in the range of 102–105 Pa. The proton transference number was determined to be 0.95 at 250 °C for 2NH4PO3–(NH4)2Mn(PO3)4 electrolyte. Fuel cells using 2NH4PO3–(NH4)2Mn(PO3)4 as an electrolyte and the Pt–C catalyst as an electrode were fabricated. Maximum power density of 16.8 mW/cm2 was achieved at 250 °C with dry hydrogen and dry oxygen as the fuel and oxidant, respectively. However, the NH4PO3–(NH4)2Mn(PO3)4 electrolyte is not compatible with the Pt–C catalyst, indicating that it is critical to develop new electrode materials for the intermediate temperature fuel cells.  相似文献   

7.
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   

8.
Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH3. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH3 is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH3/N2 mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V2O5/TiO2 catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.  相似文献   

9.
Manganese–cerium mixed oxide catalysts with different molar ratio Mn/(Mn + Ce) (0, 0.25, 0.50, 0.75, 1) were prepared by citric acid method and investigated concerning their adsorption behavior, redox properties and behavior in the selective catalytic reduction of NOx by NH3. The studies based on pulse thermal analysis combined with mass spectroscopy and FT-IR spectroscopy uncovered a clear correlation between the dependence of these properties and the mixed oxide composition. Highest activity to nitrogen formation was found for catalysts with a molar ratio Mn/(Mn + Ce) of 0.25, whereas the activity was much lower for the pure constituent oxides. Measurements of adsorption uptake of reactants, NOx (NO, NO2) and NH3, and reducibility showed similar dependence on the mixed oxide composition indicating a clear correlation of these properties with catalytic activity. The adsorption studies indicated that NOx and NH3 are adsorbed on separate sites. Consecutive adsorption measurements of the reactants showed similar uptakes as separate measurements indicating that there was no interference between adsorbed reactants. Mechanistic investigations by changing the sequence of admittance of reactants (NOx, NH3) indicated that at 100–150 °C nitrogen formation follows an Eley–Rideal type mechanism, where adsorbed ammonia reacts with NOx in the gas phase, whereas adsorbed NOx showed no significant reactivity under conditions used.  相似文献   

10.
The catalytic effect of a heteropolyacid, H4SiW12O40, on nitrobenzene (20 and 30 μM) oxidation in supercritical water was investigated. A capillary flow-through reactor was operated at varying temperatures (T=400–500 °C; P=30.7 MPa) and H4SiW12O40 concentrations (3.5–34.8 μM) in an attempt to establish global power-law rate expressions for homogenous H4SiW12O40-catalyzed and uncatalyzed supercritical water oxidation. Oxidation pathways and reaction mechanisms were further examined via primary oxidation product identification and the addition of various hydroxyl radical scavengers (2-propanol, acetone, acetone-d6, bromide and iodide) to the reaction medium. Under our experimental conditions, nitrobenzene degradation rates were significantly enhanced in the presence of H4SiW12O40. The major differences in temperature dependence observed between catalyzed and uncatalyzed nitrobenzene oxidation kinetics strongly suggest that the reaction path of H4SiW12O40-catalyzed supercritical water oxidation (average activation Ea=218 kJ/mol; k=0.015–0.806 s−1 energy for T=440–500 °C; Ea=134 kJ/mol for the temperature range T=470–490 °C) apparently differs from that of uncatalyzed supercritical water oxidation (Ea=212 kJ/mol; k=0.37–6.6 μM s−1). Similar primary oxidation products (i.e. phenol and 2-, 3-, and 4-nitrophenol) were identified for both treatment systems. H4SiW12O40-catalyzed homogenous nitrobenzene oxidation kinetics was not sensitive to the presence of OH√ scavengers.  相似文献   

11.
Selective catalytic reduction of NOx (SCR-NOx) with decane, and for comparison with propane and propene over Cu-ZSM-5 zeolite (Cu/Al 0.49, Si/Al 13.2) was investigated under presence and absence of water vapor. Decane behaves in SCR-NOx like propene, i.e. the Cu-zeolite activity increased under increasing concentration of water vapor, as demonstrated by a shift of the NOx–N2 conversion to lower temperatures, in contrast to propane, where the NOx–N2 conversion is highly suppressed. In situ FTIR spectra of sorbed intermediates revealed similar spectral features for C10H22– and C3H6–SCR-NOx, where –CHx, R–NO2, –NO3, Cu+–CO, –CN, –NCO and –NH species were found. On contrary, with propane –CHx, R–NO2, NO3, Cu+–CO represented prevailing species. A comparison of the in situ FTIR spectra (T–O–T and intermediate vibrations) recorded at pulses of propene and propane, moreover, under presence and absence of water vapor in the reaction mixture, revealed that the Cu2+–Cu+ redox cycle operates with the C3H6–SCR-NOx reactions in both presence/absence of water vapor, while with C3H8–SCR-NOx, the redox cycle is suppressed by water vapor. It is concluded that decane cracks to low-chain olefins and paraffins, the former ones, more reactive, preferably take part in SCR-NOx. It is concluded that formation of olefinic compounds at C10H22–SCR-NOx is decisive for the high activity in the presence of water vapor, while water molecules block propane activation. The increase in NOx–N2 conversion due to water vapor in C10H22–SCR-NOx should be connected with the increased reactivity of intermediates. These are suggested to pass from R–NOx → –CN → –NCO → NH3; the latter reacts with another activated NOx molecule to molecular nitrogen. The positive effect of water vapor on the NOx–N2 conversion is attributed to increased hydrolysis of –NCO intermediates.  相似文献   

12.
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   

13.
A novel TiO2/Al2O3/cordierite honeycomb-supported V2O5–MoO3–WO3 monolithic catalyst was studied for the selective reduction of NO with NH3. The effects of reaction temperature, space velocity, NH3/NO ratio and oxygen content on SCR activity were evaluated. Two other V2O5–MoO3–WO3 monolithic catalysts supported on Al2O3/cordierite honeycomb or TiO2/cordierite honeycomb support, two types of pellet catalysts supported on TiO2/Al2O3 or Al2O3, as well as three types of pellet catalysts V2O5–MoO3–WO3–Al2O3 and V2O5–MoO3–WO3–TiO2 were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO2/Al2O3 cannot be excluded.  相似文献   

14.
Selective catalytic reduction (SCR) of NO with methane in the presence of excess oxygen has been investigated over a series of Mn-loaded sulfated zirconia (SZ) catalysts. It was found that the Mn/SZ with a metal loading of 2–3 wt.% exhibited high activity for the NO reduction, and the maximum NO conversion over the Mn/SZ catalyst was higher than that over Mn/HZSM-5. NH3–TPD results of the catalysts showed that the sulfation process of the supports resulted in the generation of strong acid sites, which is essential for the SCR of NO with methane. On the other hand, the N2 adsorption and the H2–TPR of the catalysts demonstrated that the presence of the SO42− species promoted the dispersion of the metal species and made the Mn species less reducible. Such an increased dispersion of metal species suppressed the combustion reaction of CH4 by O2 and increased the selectivity towards NO. The Mn/SZ catalysts prepared by different methods exhibited similar activities in the SCR of NO with methane, indicating the importance of SO42−. The most attractive feature of the Mn/SZ catalysts was that they were more tolerant to water and SO2 poisoning than Mn/HZSM-5 catalysts and exhibited higher reversibility after removal of SO2.  相似文献   

15.
MnOx–CeO2 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 MnOx–CeO2 with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnOx–CeO2 mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnOx–CeO2 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 MnOx–CeO2 mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnOx–CeO2 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 MnOx–CeO2 support.  相似文献   

16.
Mesostructured MnOx–Cs2O–Al2O3 nanocomposites have been synthesized by reverse microemulsion method combined with hydrothermal treatment and then applied to the catalytic combustion of methane. Compared to impregnation-derived conventional MnOx/Cs2O/Com-Al2O3 catalyst, the microemulsion-derived catalyst showed higher activity and stability for methane combustion. The T10% of the fresh and of the 72 h aged MnxO–Cs2O–Al2O3 were 475 and 490 °C, respectively, recommending it as a potential candidate catalyst for application in hybrid gas turbines. The homogeneous composition of the microemulsion-derived nanocomposite catalyst can hinder the loss of Cs+ and accelerate the formation of Cs–β-alumina phase, ensuring thus higher activity and stability for methane combustion.  相似文献   

17.
An aqueous (NH4)2CO3 coprecipitation method, based on that of Groppi et al. [Appl. Catal. A 104 (1993) 101–108] was used to synthesize Sr1−xLaxMnAl11O19− hexaaluminates. These materials were first synthesized by alkoxide hydrolysis. This synthesis route requires special handling of the starting materials and is not likely to be commercially practical. The materials prepared by (NH4)2CO3 coprecipitation have similar surface areas as those prepared by the alkoxide hydrolysis method. Their CH4 oxidation activity, measured as the temperature needed for 10% conversion of methane, is higher than those prepared by alkoxide hydrolysis. The La-substantiated material, LaMnAl11O19−, shows high surface area with 19.3 m2/g after calcination at 1400°C for 2 h. It is active for CH4 oxidation with T10% at 450°C using 1% CH4 in air and 70 000 cm3/h g space velocity. The stability and activity of LaMnAl11O19− prepared by (NH4)2CO3 coprecipitation method is a simple and important step forward for the application of CH4 catalytic combustion for gas turbines.  相似文献   

18.
The development of a catalytically active filter element for combined particle separation and NOx removal or VOC total oxidation, respectively, is presented. For NOx removal by selective catalytic reduction (SCR) a catalytic coating based on a TiO2–V2O5–WO3 catalyst system was developed on a ceramic filter element. Different TiO2 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 TiO2-impregnated sintered filter element cylinders exhibit BET surface areas in the range between 0.5 and 1.3 m2/g. Selected TiO2-impregnated filter element cylinders of high BET surface area were catalytically activated by impregnation with a V2O5 and WO3 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 TiO2-impregnated filter element support was catalytically activated with a Pt/V2O5 system. Complete oxidation of propene with 100% selectivity to CO2 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   

19.
The aim of this work was to identify the optimum synthesis conditions and the most effective technique for noble metal deposition in a perovskite/palladium-based catalyst for natural gas combustion. The solution combustion synthesis (SCS) of perovskite/zirconia-based materials was investigated, by starting from metal nitrates/glycine mixtures. Characterization and catalytic activity tests were performed on as-prepared powders and then repeated after calcination for 2 h at 900 °C in calm air. Calcination appeared to be beneficial in that, despite lowering the specific surface area, it promoted the simultaneous crystallization of both LaMnO3 and ZrO2 and the half-conversion temperature (T50), regarded as an index of catalytic activity, was lowered. Two phases, both active towards methane oxidation – lanthanum manganate and palladium oxide – were combined so as to evaluate their synergism in terms of catalytic activity. Pd was therefore added either via incipient wetness impregnation on LaMnO3·2ZrO2 or through a one-step SCS-based route. Characterization and catalytic activity tests followed suit. Optimal composition and preparation routes were found: T50 was lowered from 507 °C – pure LaMnO3 prepared via SCS – to 432 °C attained with a 2% (w/w) Pd load on pre-calcined LaMnO3·2ZrO2.  相似文献   

20.
Ion-exchanged pillared clays (PILCs) were studied as catalysts for selective catalytic reduction (SCR) of NO by ethylene. Three most important pillared clays, Al2O3-PILC (or Al-PILC), ZrO2-PILC (or Zr-PILC) and TiO2-PILC (or Ti-PILC), were synthesized. Cation exchanges were performed to prepare the following catalysts: Cu–Ti-PILC, Cu–Al-PILC, Cu–Zr-PILC, Cu–Al–Laponite, Fe–Ti-PILC, Ce–Ti-PILC, Ce–Ti-PILC, Co–Ti-PILC, Ag–Ti-PILC and Ga–Ti-PILC. Cu–Ti-PILC showed the highest activities at temperatures below 370°C, while Cu–Al-PILC was most active at above 370°C, and both catalysts were substantially more active than Cu-ZSM-5. No detectable N2O was formed by all of these catalysts. H2O and SO2 only slightly deactivated the SCR activity of Cu–Ti-PILC, whereas severe deactivation was observed for Cu-ZSM-5. The catalytic activity of Cu–Ti-PILC was found to depend on the method and amount of copper loading. The catalytic activity increased with copper content until it reached 245% ion-exchange. The doping of 0.5 wt% Ce2O3 on Cu–Ti-PILC increased the activities from 10% to 30% while 1.0 wt% of Ce2O3 decreased the activity of Cu–Ti-PILC due to pore plugging. Cu–Ti-PILC was found to be an excellent catalyst for NO SCR by NH3, but inactive when CH4 was used as the reducing agent. Subjecting the Cu–Ti-PILC catalyst to 5% H20 and 50 ppm SO2 at 700°C for 2 h only slightly decreased its activity. TPR results showed that the overexchanged (245%) PILC sample contained Cu2+, Cu+ and CuO. The TPR temperatures for the Cu–Ti-PILC were substantially lower than that for Cu-ZSM-5, indicating easier redox on the PILC catalyst and hence higher SCR activity.  相似文献   

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