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1.
Reaction activities of several developed catalysts for NO oxidation and NOx (NO + NO2) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co3O4 based catalysts are the most active ones for both NO oxidation and NOx reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co3O4 catalyst, the effects of calcination temperatures, SO2 concentration, optimum SV for 50% conversion of NO to NO2 were determined. Also, Co3O4 based catalysts (Co3O4-WO3) exhibit significantly higher conversion than all the developed DeNOx catalysts (supported/unsupported) having maximum conversion of NOx even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N2O formation over Co3O4-WO3 catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N2O over all the catalysts. The effect of SO2 concentration on NOx reduction is found to be almost negligible may be due to the presence of WO3 that resists SO2 oxidation.  相似文献   

2.
The behavior of the selective catalytic reduction of nitrogen oxides (NOx) assisted by a dielectric barrier discharge was investigated. The principal function of the dielectric barrier discharge in the present system is to generate ozone, which is continuously fed to a chamber where the ozone and NO-rich exhaust gas (NO forms the large majority of NOx) are mixed. In the ozonization chamber, a part of NO contained in the exhaust gas is oxidized to NO2, and then the mixture of NO and NO2 enters the catalytic reactor. The ozonization method proposed in this study was found to be more energy-efficient for the oxidation of NO to NO2 than the typical nonthermal plasma process. The degree of NO oxidation was approximately equal to the amount of ozone added to the exhaust gas, implying that the decomposition of ozone into molecular oxygen was relatively slow, compared to its reaction with NO. When the exhaust gas was first treated by ozone to produce a mixture of NO and NO2, a remarkable enhancement in the catalytic reduction of nitrogen oxides was observed. Neither NO3 nor N2O5 was formed in the present system, but small amounts of ozone and N2O (less than 5 ppm) were detected in the outlet gas.  相似文献   

3.
以256 m2烧结机O3氧化烧结烟气中NO过程为研究对象,采用CFD数值模拟方法考察了含O3喷射气体与烧结烟气流动及NO低温氧化特性。通过与76步复杂反应机理的对比验证了11步简化机理的适用性,分析了反应温度、O3/NO摩尔比以及O3分布特性对NO氧化效率和不同价态NO x 转化率的影响规律。通过对简单结构反应器的模拟结果表明:NO3稳定性较差,烟道内主要氧化产物为NO2与N2O5;随反应温度升高,NO氧化效率基本保持不变,NO2转化率提高且提升速率逐渐增大而N2O5呈相反规律;随O3/NO摩尔比增大,NO氧化效率提高但提升速率逐渐减小,NO2转化率先增大后在摩尔比高于1.25时开始减小,而各工况均产生N2O5且生成量逐渐增大,其原因为射流核心区可提供高O3/NO摩尔比条件;通过优化O3分布器结构改善O3与烟气接触与混合条件,O3与NO摩尔比为1.0、停留时间为0.87 s时NO氧化率可提高约12.8%,摩尔比为2.0、停留时间为1.73 s时N2O5转化率可提高约15.6%。  相似文献   

4.
The selective catalytic reduction of NO+NO2 (NOx) at low temperature (180–230°C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH3/NOx and NO/NO2 inlet ratios has been studied. High NOx conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N2O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNOx activity, with no detectable ammonia slip and a low N2O formation when NH3/NOx inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH3/O2, NO2/NH3/O2 and NO/NO2/NH3/O2 feed mixtures indicated that the presence of NO2 as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N2O formation. When NO was also present, N2O formation was not observed.  相似文献   

5.
The simultaneous adsorption of SO2 and NOx on Na-γ-alumina was studied by means of step experiments in a fixed bed plug flow reactor at 387 K and atmospheric pressure. Typically the molar composition of the feed gas was 1.5% SO2, 1% O2, 4000 ppm NO, 500 ppm NO2, and Ar. First the adsorption behavior of the pure components was measured. SO2 and NO2 adsorb easily, whereas NO and O2 do not adsorb. Moreover there is no influence of O2 on the adsorption behavior of the pure components.

NO and O2 adsorption require the simultaneous presence of SO2, NO, and O2. The NO and O2 adsorption rate is enhanced by an increasing SO2/NO ratio. The total amount of SO2 adsorbed is not affected by the simultaneous adsorption of NO and O2. However, NO2 adsorption increases the SO2 adsorption capacity. In the presence of NO2 most of the adsorbed NOx is released as NO.  相似文献   


6.
The release and reduction of NOx in a NOx storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O2 pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al2O3 catalyst, the time profiles of several gas products, NO, N2, NH3 and H2O, were obtained as a result of the release and reduction of NOx caused by H2 injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO3)2/cordierite plate, the release and reduction of NOx on Pt/Ba/Al2O3 catalyst that stored NOx took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N2 by H2 pulse injection. When this H2 pulse was injected in a large amount, NO was reduced to NH3 instead of N2.

A only small amount of H2O was detected because of the strong affinity for alumina support. We can analyze the NOx regeneration process to separate two steps of the NOx release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NOx release increased as temperature increase.  相似文献   


7.
The influence of NO2 on the selective catalytic reduction (SCR) of NO with ammonia was studied over Fe-ZSM5 coated on cordierite monolith. NO2 in the feed drastically enhanced the NOx removal efficiency (DeNOx) up to 600 °C, whereas the promoting effect was most pronounced at the low temperature end. The maximum activity was found for NO2/NOx = 50%, which is explained by the stoichiometry of the actual SCR reaction over Fe-ZSM5, requiring a NH3:NO:NO2 ratio of 2:1:1. In this context, it is a special feature of Fe-ZSM5 to keep this activity level almost up to NO2/NOx = 100%. The addition of NO2 to the feed gas was always accompanied by the production of N2O at lower and intermediate temperatures. The absence of N2O at the high temperature end is explained by the N2O decomposition and N2O-SCR reaction. Water and oxygen influence the SCR reaction indirectly. Oxygen enhances the oxidation of NO to NO2 and water suppresses the oxidation of NO to NO2, which is an essential preceding step of the actual SCR reaction for NO2/NOx < 50%. DRIFT spectra of the catalyst under different pre-treatment and operating conditions suggest a common intermediate, from which the main product N2 is formed with NO and the side-product N2O by reaction with gas phase NO2.  相似文献   

8.
The selective catalytic reduction of NOx by methane on noble metal-loaded sulfated zirconia (SZ) catalysts was studied. Ru, Rh, Pd, Ag, Ir, Pt, and Au-loaded sulfated zirconia catalysts were compared with the intact sulfated zirconia. For the NO–CH4–O2 reaction, Ru, Rh, Pd, Ir, and Pt showed promotion effect on NOx reduction, while for the NO2–CH4–O2 reaction, only Rh and Pd showed promotion effect. Over intact and Rh, Pd, Ag, and Au-loaded sulfated zirconia, NOx conversion in NO2–CH4–O2 reaction was significantly higher than that in NO–CH4–O2 reaction, while clear difference was not observed over Ru, Ir, and Pt-loaded sulfated zirconia. Comparison of [NO2]/([NO]+[NO2]) in the effluent gases in NO–O2 and NO2–O2 reactions showed that Ru, Ir, and Pt has high activity for NO oxidation under the reaction conditions. These facts suggest that effects of these metals toward NOx reduction by methane can be categorized into the following three groups: (i) low activity for NO oxidation to NO2, and high activity for NO2 reduction to N2 (Pd, Rh); (ii) high activity for NO oxidation to NO2, and low activity for NO2 reduction to N2 (Ru, Ir, Pt); (iii) low activity for both reactions (Ag, Au). To confirm these suggestions, combination of these metals were investigated on binary or physically-mixed catalysts. The combination of Pd or Rh with Pt or Ru gave high activity for the selective reduction of NOx by methane.  相似文献   

9.
In this work, a kinetic model is constructed to simulate sulfur deactivation of the NOx storage performance of BaO/Al2O3 and Pt/BaO/Al2O3 catalysts. The model is based on a previous model for NOx storage under sulfur-free conditions. In the present model the storage of NOx is allowed on two storage sites, one for complete NOx uptake and one for a slower NOx sorption. The adsorption of SOx is allowed on both of these NOx storage sites and on one additional site which represent bulk storage. The present model is built-up of six sub-models: (i) NOx storage under sulfur-free conditions; (ii) SO2 storage on NOx storage sites; (iii) SO2 oxidation; (iv) SO3 storage on bulk sites; (v) SO2 interaction with platinum in the presence of H2; (vi) oxidation of accumulated sulfur compounds on platinum by NO2. Data from flow reactor experiments are used in the implementation of the model. The model is tested for simulation of experiments for NOx storage before exposure to sulfur and after pre-treatments either with SO2 + O2 or SO2 + H2. The simulations show that the model is able to describe the main features observed experimentally.  相似文献   

10.
The adsorption of HCN on, its catalytic oxidation with 6% O2 over 0.5% Pt/Al2O3, and the subsequent oxidation of strongly bound chemisorbed species upon heating were investigated. The observed N-containing products were N2O, NO and NO2, and some residual adsorbed N-containing species were oxidized to NO and NO2 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 N2 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 N2O is located between 200 and 250 °C, while raising the reaction temperature increases the proportion of NOx in the products. The co-feeding of H2O and C3H6 had little, if any effect on the total HCN conversion, but C3H6 addition did increase the conversion to NO and decrease the conversion to NO2, perhaps due to the competing presence of adsorbed fragments of reductive C3H6. Evidence is also presented that introduction of NO and NO2 into the reactant gas mixture resulted in additional reaction pathways between these NOx species and HCN that provide for lean-NOx reduction coincident with HCN oxidation.  相似文献   

11.
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   

12.
Free energy minimization calculations are used to determine the thermodynamic equilibrium concentrations of NOx and other species in stoichiometric and lean gas mixtures over a range of temperatures and compositions. Under lean (excess N2 and O2) conditions, the NO decomposition (NO↔(1/2)N2+(1/2)O2) and NO oxidation (NO+(1/2)O2↔NO2) equilibria impose lower bounds on the NOx concentrations achievable by thermodynamic equilibration or NOx decomposition, and these equilibrium NOx concentrations can be practically significant. Assuming a perfect isothermal catalyst acting on a representative diesel exhaust stream collected over the federal test procedure (FTP) cycle, equilibrium NOx levels exceed upcoming California Low Emission Vehicle II (LEV-II) and Tier II NOx emissions standards for automobiles and trucks at temperatures above approximately 800 K. Consideration of a perfect adiabatic catalyst acting on the same diesel exhaust shows that equilibrium NOx values can fall below NOx emissions standards at lower temperatures, but to achieve these low concentrations would require the catalyst to attain 100% approach to equilibrium at very low temperatures. It is concluded that NOx removal based on a thermodynamic equilibrating catalyst under lean exhaust conditions is not practically viable for automotive application, and that to achieve upcoming NOx standards will require selective NOx catalysts that vigorously promote NOx reactions with reductant and do not promote NO decomposition or oxidation. Finally, the ability of a selective NOx catalyst system to reduce NOx concentrations to or below thermodynamic equilibrium values is proposed as a useful measure for selective catalytic reduction (SCR) activity.  相似文献   

13.
The heterogeneous reactivity of NOx and SO2 with carbon has been investigated with FT-IR spectroscopy. The interaction between NO and SO2 on carbon surface have been studied in the presence and in the absence of oxygen. Thermal stabilities of surface structures, formed as a result of NOx and SO2 chemisorption have been determined by means of FT-IR spectroscopy. During the reaction of NO/O2 mixture with carbon the surface species, including C–NO2, C–ONO, C–NCO and anhydride structures are formed. It has been found that SO2 retards the oxidation reaction of carbon by oxygen. The oxidation of SO2 on carbon was found to be greatly enhanced by the presence of NO + O2 mixture. The adsorption capacity of cellulose based carbon, catalytic NOx decomposition and TPD was studied using a fixed bed flow reactor.  相似文献   

14.
The activity of several catalysts are studied in the soot combustion reaction using air and NO/air as oxidising agents. Over Al2O3-supported catalysts NO(g) is a promoter for the combustion reaction with the extent of promotion depending on the Na loading. Over these catalysts SO42− poisons this promotion by preventing NO oxidation through a site blocking mechanism. SiO2 is unable to adsorb NO or catalyse its oxidation and over SiO2-supported Na catalysts NO(g) inhibits the combustion reaction. This is ascribed to a competition between NO and O2. Over Fe-ZSM-5 catalysts the presence of a NOx trapping component does not increase the combustion of soot in the presence of NO(g) and it is proposed that this previously reported effect is only seen under continuous NOx trap operation as NO2 is periodically released during regeneration and thus available for soot combustion. Experiments during which the [NO](g) is varied show that CO, rather than an adsorbed carbonyl-like intermediate, is formed upon reaction between NO2 (the proposed oxygen carrier) and soot.  相似文献   

15.
On an anodic alumina supported silver catalyst with a low Ag loading (1.68 wt.%), NOx (NO/He, NO/O2/He, NO2/He) adsorption measurements and NOx-temperature programmed decomposition (TPD)/temperature programmed surface-reaction (TPSR) measurements in different gas streams (He, C3H6/He, C3H6/O2/He) were conducted to investigate the formation, consumption and reactivity of surface adsorbed NOx species.

During NO adsorption, no noticeable uptake of NO was detected. Introducing oxygen greatly improved the formation of ads-NOx species. A greater quantity of surface nitrate species was found after NO2 adsorption, accompanied with gaseous NO release. The result of TPSR demonstrates the surface nitrate species can be effectively and preferentially reduced by propene. When introducing oxygen into the propene gas stream of TPSR test, the significantly increased amount of reacted nitrate undoubtedly shows the importance of oxygen in activating propene. The pathway for the selective reduction of NOx in the presence of excess oxygen is proposed to pass through the selective reduction of the adsorbed nitrate species with the activated propene.

The enhanced NOx conversion when replacing NO with NO2 was attributed to the stronger NOx adsorption capacity and oxidation ability of NO2, than those for NO. With increasing oxygen concentration, the difference between NO and NO2 would gradually decrease, and finally disappear in a high excess of oxygen.  相似文献   


16.
In this paper, the effect of CO2 and H2O on NOx storage and reduction over a Pt–Ba/γ-Al2O3 (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO2 and H2O, NOx is stored on BaCO3 sites only. Moreover, H2O inhibits the NO oxidation capability of the catalyst and no NO2 formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N2 as well as complete regeneration of stored NO. In the presence of CO2, NO is oxidized into NO2 and more NOx is stored as in the presence of H2O, resulting in 30% barium utilization. Bulk barium sites are inactive in NOx trapping in the presence of CO2·NH3 formation is seen in the rich phase and the selectivity towards N2 is 83%. Ba(NO3)2 is always completely regenerated during the subsequent rich phase. In the absence of CO2 and H2O, both surface and bulk barium sites are active in NOx storage. As lean/rich cycling proceeds, the selectivity towards N2 in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NOx storage.  相似文献   

17.
A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study. The flue gas containing 200 mg·m-3 NO, 1000-4000 mg·m-3 SO2, 3%-9% O2, and 10%-20% CO2 was first oxidized by O3 and then absorbed by ammonia in a bubbling reactor. Increasing the ammonia concentration or the SO2 content in flue gas can promote the absorption of NOX and extend the effective absorption time. On the contrary, both increasing the absorbent temperature or the O2 content shorten the effective absorption time of NOX. The change of solution pH had substantial influence on NOX absorption. In the presence of CO2, the NOX removal efficiency reached 89.2% when the absorbent temperature was raised to 60 °C, and the effective absorption time can be maintained for 8 h, which attribute to the buffering effect in the absorbent. Besides, both the addition of Na2S2O3 and urea can promote the NOX removal efficiency when the absorbent temperature is 25 °C, and the addition of Na2S2O3 had achieved better results. The advantage of adding Na2S2O3 became less evident at higher absorbent temperature and coexistence of CO2. In all experiments, SO2 removal efficiency was always above 99%, and it was basically not affected by the above factors.  相似文献   

18.
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   

19.
This study addresses the catalytic reaction of NOx and soot into N2 and CO2 under O2-rich conditions. To elucidate the mechanism of the soot/NOx/O2 reaction and particularly the role of the catalyst -Fe2O3 is used as model sample. Furthermore, a series of examinations is also made with pure soot for reference purposes. Temperature programmed oxidation and transient experiments in which the soot/O2 and soot/NO reaction are temporally separated show that the NO reduction occurs on the soot surface without direct participation of the Fe2O3 catalyst. The first reaction step is the formation of CC(O) groups that is mainly associated with the attack of oxygen on the soot surface. The decomposition of these complexes leads to active carbon sites on which NO is adsorbed. Furthermore, the oxidation of soot by oxygen provides a specific configuration of active carbon sites with suitable atomic orbital orientation that enables the chemisorption and dissociation of NO as well as the recombination of two adjacent N atoms to evolve N2. Moreover, carbothermal reaction, high resolution transmission electron microscopy and isotopic studies result in a mechanistic model that describes the role of the Fe2O3 catalyst. This model includes the dissociative adsorption of O2 on the iron oxide, surface migration of the oxygen to the contact points of soot and catalyst and then final transfer of O to the soot. Moreover, our experimental data suggest that the contact between both solids is maintained up to high conversion levels thus resulting in continuous oxygen transfer from catalyst to soot. As no coordinative interaction of soot and Fe2O3 catalyst is evidenced by diffuse reflectance infrared Fourier transform spectroscopy a van der Waals type interaction is supposed.  相似文献   

20.
Nitric oxide and nitric dioxide compounds (NOx) present in stack gases from nitric acid plants are usually eliminated by selective catalytic reduction (SCR) with ammonia. In this process, small quantities of nitrous oxide (N2O) are produced. This undesirable molecule has a high greenhouse gas potential and a long lifetime in the atmosphere, where it can contribute to stratospheric ozone depletion. The influence of catalyst composition and some operating variables were evaluated in terms of N2O formation, using V2O5/TiO2 catalysts. High vanadia catalyst loading, nitric oxide inlet concentration and reaction temperature increase the generation of this undesirable compound. The results suggest that adsorbed ammonia not only reacts with NO via SCR, but also with small quantities of oxygen activated by the presence of NO. The mechanism proposed for N2O generation at low temperature is based on the formation of surface V–ON species which may be produced by the partial oxidation of dissociatively adsorbed ammonia species with NO + O2 (eventually NO2). When these active sites are in close proximity they can interact to form an N2O molecule. This mechanism seems to be affected by changes in the active site density produced by increasing the catalyst vanadia loading.  相似文献   

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