基于CFD模拟的臭氧低温氧化烧结烟气中NO过程分析

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%。     

The selective catalytic reduction of nitrogen oxides by methane on noble metal-loaded sulfated zirconia

The selective catalytic reduction of NO_x 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 NO_x 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, NO_x 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 NO_x 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 NO_x by methane.     

Partial oxidation of light alkanes by NOx in the gas phase

Partial oxidations of CH₄, C₂H₆, C₃H₈, and iso-C₄H₁₀ with O₂ were promoted by addition of NO in the gas phase. The addition of NO increased the conversion rate of alkanes and decreased the initiation temperatures for the reactions. Moreover, selectivities and yields to oxygenates, aldehydes, ketones and alcohols, were remarkably improved by the addition of NO. The maxima of one-pass yields of oxygenates were 7% for CH₄, 11% for C₂H₆, 13% for C₃H₈, and 29% for iso-C₄H₁₀. It is suggested that NO₂ produced from NO and O₂ is the initiator for the oxidation of light alkanes. Alkyl nitrite was proposed as the reaction intermediate for the formation of oxygenates. The alkyl nitrite decomposes into oxygenates and NO that works as catalyst for the activation of O₂ and the oxidation of alkanes.     

Catalytic oxidation of HCN over a 0.5% Pt/Al2O3 catalyst

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 NO_x 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 NO_x species and HCN that provide for lean-NO_x reduction coincident with HCN oxidation.     

Understanding the activation mechanism induced by NOx on the performances of VOx/TiO2 based catalysts in the total oxidation of chlorinated VOCs

A previous investigation of the chlorobenzene combustion activity of VO_x/TiO₂, VO_x–WO_x/TiO₂ and VO_x–MoO_x/TiO₂ catalysts in the presence of NO pointed out the activation effect of NO. The suggested three-step mechanism based on catalytic performances data only was: (1) chlorobenzene is oxidized on the surface of the VO_x phase (as described by Mars–van Krevelen), (2) NO gets oxidized to NO₂, mainly on WO_x and MoO_x, and (3) the in situ produced NO₂ assists O₂ in the reoxidation of the VO_x phase thus speeding up the oxidation step of the Mars–van Krevelen mechanism. The latter effect macroscopically corresponds to the observed increase of chlorobenzene conversion. This contribution aims at validating this hypothetical mechanism by pointing out the favourable occurrence of an oxidation of NO to NO₂ on the WO_x and MoO_x phases and by pointing out the higher efficiency of NO₂ than O₂ to reoxidize the reduced VO_x sites. In addition, the present contribution clearly demonstrates that, in the absence of NO, the chlorobenzene total oxidation occurred following the Mars–van Krevelen mechanism. Moreover, a thorough characterization of the oxidation state of the vanadium proving that the improvement of the catalyst activity brought by the simultaneous presence of NO and O₂ is linked to the stronger reoxidation of the VO_x active phase. Furthermore, plotting all the catalytic activity data versus the mean vanadium oxidation level clearly depicts, for the first time, the strong dependence between them. Under a mean vanadium oxidation level of 4.82 the catalyst is inactive while above 4.87 the activity is stabilized at a high level of conversion independent of the vanadium oxidation level.     

Catalytic effect of platinum on the kinetics of carbon oxidation by NO2 and O2

The effect of a commercial Pt/Al₂O₃ catalyst on the oxidation by NO₂ and O₂ of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O₂ and NO₂ is observed. However, in presence of NO₂–O₂ mixture, it is found that besides the well established catalytic reoxidation of NO into NO₂, Pt also exerts a catalytic effect on the cooperative carbon–NO₂–O₂ oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO₂ leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.     

Mass spectra of negative ions in air-like gas mixtures at atmospheric pressure

We have obtained mass spectra of negative ions produced by rays in artificial air at atmospheric pressure (N₂: 80%, O₂: 20%, H₂O: 20–1500 ppm, CO₂: 0.2–300 ppm, NO, NO₂ 0.02 ppm). We observed two main categories: hydrates built on simple ions (O₂⁻, O₃⁻, OH⁻, CO₃⁻, CO₄⁻, HCO₃⁻, NO₂⁻, NO₃⁻), hydrates built on complex ions (NO_x⁻, HNO_γ, HCO₃⁻HNO_x, x = 2,3; Y = 2, 3). For high values of hygrometry, CO₂ content and ageing time (5 msec) we observe the disappearance of O₂⁻, O₃⁻, OH⁻ hydrates whereas the major part of the spectrum consists of complex ions.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Molecule sieving catalysts for NO reduction with hydrocarbons in exhaust of lean burn gasoline and diesel engines

NO oxidation catalysts with small pores and low hydrocarbon oxidation activity owing to molecular sieving were prepared by dispersing platinum in the pores of ferrierite and chabazite zeolites. These small pore platinum zeolite crystals were physically mixed with large pore silver mordenite zeolite crystals and evaluated as HC-SCR catalysts for selective catalytic reduction of NO in a synthetic gas mixture doped with octane or isooctane, mimicking exhaust from lean burning engines with unburned hydrocarbons. A synergetic effect on N₂ formation and hydrocarbon efficiency was obtained in these physical zeolite mixtures. In the pores of the small pore zeolite where the diffusion of NO, O₂ and NO₂ molecules with small kinetic diameters was rapid, NO was effectively oxidized by the platinum into NO₂, while the small window apertures suppressed the diffusion and reaction of the hydrocarbon. The silver plated large pore zeolite catalyzed the reaction between the NO₂ formed in the small pore zeolite and the hydrocarbon. The importance of molecular sieving was demonstrated in experiments with permutation of pore sizes and catalytic functions.     

Effect of gas composition on nitric oxide removal from simulated flue gas with DBD-NPC method

A new method for nitric oxide (NO) removal was developed by combining dielectric barrier discharge (DBD) and negative pulse corona (NPC). The effects of gas composition (O₂, CO₂, and H₂O) on NO removal were investigated with this method, and the effect of alcohols (methanol and ethanol) addition on NO removal was also investigated as well as the reaction mechanisms to enhance the NO removal efficiency. The experimental results showed that O₂, CO₂, and H₂O had obvious inhibition effects on NO removal, and the negative effects were in the following order:O₂ > CO₂ > H₂O. The addition of methanol or ethanol in the reaction system could mitigate the negative effects of O₂, CO₂, and H₂O on NO removal, and also eliminated the production of NO₂. The positive effect of alcohols addition with DBD-NPC denitration method was also validated in the simulated flue gas, in which the NO_x (NO, NO₂) was mainly converted into N².     

Engineering practice and economic analysis of ozone oxidation wet denitrification technology

SO₂ and NO emitted from coal-fired power plants have caused serious air pollution in China. In this study, a test system for NO oxidation using O₃ is established. The basic characteristics of NO oxidation and products forms are studied. A separate test system for the combined removal of SO₂ and NO_x is also established, and the absorption characteristics of NO_x are studied. The characteristics of NO oxidation and NO_x absorption were verified in a 35 t·h^-1 industrial boiler wet combined desulfurization and denitrification project. The operating economy of ozone oxidation wet denitrification technology is analyzed. The results show that O₃ has a high rate and strong selectivity for NO oxidation. When O₃ is insufficient, the primary oxidation product is NO₂. When O₃ is present in excess, NO₂ continues to get oxidized to N₂O₅ or NO₃. The removal efficiency of NO₂ in alkaline absorption system is low (only about 15%). NO_x removal efficiency can be improved by oxidizing NO_x to N₂O₅ or NO₃ by increasing ozone ratio. When the molar ratio of O₃/NO is 1.77, the NO_x removal efficiency reaches 90.3%, while the operating cost of removing NO_x per kilogram is 6.06 USD (NO₂).     

Oxidation state of palladium as a factor controlling catalytic activity of Pd/SiO2–Al2O3 in propane combustion

The oxidation state of palladium on SiO₂–Al₂O₃ used for propane combustion was examined by XPS and XRD, and the correlation of the catalytic activity with the oxidation state of palladium was systematically studied. The propane conversion over 5 wt% Pd/SiO₂–Al₂O₃ was measured in the range 1.0≤S≤7.2 (S is defined as [O₂]/5[C₃H₈] based on stoichiometric ratio). The propane conversion strongly depended on the S value and reached the maximum at S=5.5. The oxidation state of palladium also changed with the S value; palladium particles were more oxidized under the reaction mixture of higher S value. On the sample used for the reaction at S=5.5, both of metallic palladium and palladium oxide were found. It is concluded that partially oxidized palladium which has optimum ratio of metallic palladium to palladium oxide shows the highest catalytic activity in propane combustion.     

Methanol formation from methane partial oxidation in CH4–O2–NO gaseous phase at atmospheric pressure

The reaction condition for high yield of methanol in a gaseous reaction between methane and oxygen in the presence of NO at atmospheric pressure was explored. Methane partial oxidation without NO (CH₄–O₂) gave only 1% conversion of methane at 966 K. The addition of NO led to a remarkable increase in methane conversion and to high selectivity to C₁-oxygenates. The conversion of methane attained 10% at 808 K in the presence of NO (0.5%) where the selectivities to methanol and formaldehyde were 22.1 and 24.1%, respectively. Nitromethane and carbon oxides were also observed in the product gas. The amount of nitromethane was almost equal and/or near to that of initial NO. The carbon monoxide produced was several times higher than carbon dioxide. Influences of NO concentration, ratio of methane to oxygen, water vapor, and dilution with helium gas on product distribution were measured. Low concentration of NO (0.35–0.55%) was favorable for methanol formation. High selectivity to methanol was obtained at low value of the ratio of methane to oxygen (2.0–3.0) or low concentration of dilution gas (<16%). The NO₂ added promoted methane partial oxidation and selectivity to methanol. Therefore, it was assured that NO_x promoted the formation of CH₃√ and CH₃O√ in the gas phase reaction for CH₄–O₂–NO.     

常温下碳基活性材料催化氧化NO的研究进展

针对常温、含高浓度O₂ 的NO污染气体排放控制,典型的选择性催化还原（SCR）技术已不再适用。以碳基活性材料为催化剂的NO常温催化氧化技术得到了广泛关注,该技术在常温和高浓度O₂条件下将NO氧化为NO₂,并以硝酸或硝酸盐形式加以回收利用,因此具有环保和经济双重效益,应用前景广阔。本文简要综述了碳基活性材料常温催化氧化NO的研究进展,阐述了NO催化氧化机理,介绍了碳基活性材料的表面物化特性和反应条件（O₂浓度、NO浓度、GHSV、反应温度、水蒸气和催化剂粒径等）对催化氧化NO的影响,以及活性炭、活性炭纤维、碳纳米纤维、炭干凝胶、金属负载碳基活性材料、炭化污泥等不同碳基活性材料的催化特性,总结并展望了未来碳基活性材料低温催化氧化NO的发展方向。     

The effect of oxygen concentration on the reduction of NO with propylene over CuO/γ-Al2O3

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

The combustion of carbon particulates using NO/O2 mixtures: The influence of SO4 and NOx trapping materials

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 NO_x 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 NO_x 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.     

Preparation of supported Pt-M catalysts (M = Mo and W) from anion-exchanged hydrotalcites and their catalytic activity for low temperature NO-H2-O2 reaction

The NO-H₂-O₂ reaction was studied over supported bimetallic catalysts, Pt-Mo and Pt-W, which were prepared by coexchange of hydrotalcite-like Mg-Al double layered hydroxides by Pt(NO₂)₄²⁻, MoO₄²⁻, and/or WO₄²⁻ and subsequent heating at 600 °C in H₂. The Pt–Mo interaction could obviously be seen when the catalyst after reduction treatment was exposed to a mixture of NO and H₂ in the absence of O₂. The Pt-HT catalyst showed the almost complete NO conversion at 70 °C, whereas the Pt-Mo-HT showed a negligible conversion. Upon exposure to O₂, however, Pt-Mo-HT exhibited the NO conversion at the lowest temperature of ≥30 °C, compared to ≥60 °C required for Pt-HT. EXAFS/XANES, XPS and IR results suggested that the role of Mo is very sensitive to the oxidation state, i.e., oxidized Mo species residing in Pt particles are postulated to retard the oxidative adsorption of NO as NO₃ and promote the catalytic conversion of NO to N₂O at low temperatures.     

富氧气氛下改性生物质焦脱汞的氧化机理

富氧燃烧作为新型燃烧方式可以有效减少CO₂排放,提高燃烧效率,与传统燃烧方式相比,烟气组分也产生较大的变化。玉米秸秆焦可以作为吸附剂在燃烧后阶段对汞进行脱除。本文采用1% NH₄Cl溶液浸渍的玉米秸秆焦为吸附剂,在富氧气氛下探究NO及O₂对汞氧化脱除机理。文中指出玉米秸秆焦经浸渍改性处理后,其表面孔隙结构更加丰富,比表面积以及总孔容积增大。同时,改性后表面官能团的数量大大增加,尤其是含氧的官能团,对汞的吸附起着重要作用。富氧气氛下NO与生物质焦表面的O₂和含氧基团反应生成具有氧化作用的NO₂,与零价汞反应促进汞的去除。NO和O₂共存时对零价汞的氧化有更明显的促进作用。O₂含量的增加也会促进生物质焦对汞的吸附,这主要是由于O₂的强氧化作用导致,与零价汞发生非均相氧化反应生成HgO。此外,含氧官能团化学键的断裂也为汞的氧化提供了氧自由基团。     

The bifunctional reaction pathway and dual kinetic regimes in NOx SCR by methane over cobalt mordenite catalysts

The pathway for selective reduction of NO_x by methane over Co mordenite cataysts has been studied by comparing the rates of the individual reactions (NO oxidation, CH₄ oxidation, NO₂ reduction) with that of the combined reaction (NO + O₂ + CH₄). Co⁽⁺²⁾ was exchanged into H-MOR and Na-MOR to give catalysts with different metal loading and number of support protons. Additionally, exchanged Co⁽⁺²⁾ ions were precipitated with NaOH to produce dispersed cobalt oxide on Na-MOR. The NO oxidation rate is the same for ion exchanged Co⁽⁺²⁾ ions in H-MOR and Na-MOR, but the rate of Co⁽⁺²⁾ ions is much lower than that of cobalt oxide. NO oxidation equilibrium is obtained only for those catalysts with high metal loading, cobalt oxide or run at low GHSV. Under the conditions of selective catalytic reduction, methane oxidation by O₂ is low for all catalysts. The turnover frequency of Co on Na-MOR, however, is higher than that on H-MOR. The rate of NO₂ reduction to N₂ is directly proportional to the number of support acid sites and independent of the amount of Co. Comparison of the rates and selectivities for the individual reactions with the combined reaction of NO + O₂ + CH₄ indicates that there are two types of catalysts. For the first, the NO oxidation is in equilibrium and the rate determining step is reduction of NO₂. For these catalysts, the rate (and selectivity) for formation of N₂ is identical from NO + O₂ + CH₄ and NO₂ + CH₄. These catalysts have high metal loading and few acid sites. Nevertheless, the rate of N₂ formation increases with increasing number of protons. For the second type of catalyst, NO oxidation is not in equilibrium and is the rate limiting step. For these catalysts the rate of N₂ formation increases with increasing metal loading. Neither catalyst type, however, is optimized for the maximum formation of N₂. By using a mixture of catalysts, one with high NO oxidation activity and one with a large number of Brønsted acid sites, the rate of N₂ is greater than the weighted sum of the individual catalysts. The current results support the proposal that the pathway for selective catalytic reduction is bifunctional where metal sites affect NO oxidation, while support protons catalyze the formation of N₂.     

Investigation of simultaneous adsorption of SO2 and NOx on Na-γ-alumina with transient techniques

The simultaneous adsorption of SO₂ and NO_x 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 NO_x is released as NO.