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.     

常温下沥青基活性炭纤维对NO的催化氧化性能

以4种比表面积不同的沥青基活性炭纤维为材料,研究了常温下对模拟空气气氛中体积分数为50×10^-6的NO的催化氧化性能,并采用氮吸附法、Raman光谱和红外光谱对活性炭纤维进行了表征。结果表明,活性炭纤维可将NO部分催化转化为NO₂,较低比表面积的活性炭纤维因为其较窄的孔径分布和较大的类石墨微晶而有利于对NO的催化氧化。     

Catalytic oxidation of carbon by palladium

The oxidation of carbon catalysed by Pd was studied by thermogravimetric and electron microscopy techniques. Powdered carbon samples loaded with various amounts of Pd have been reacted with oxygen at atmospheric pressure in the temperature range 523–723 K. Reaction rate was observed to increase with temperature, low oxygen partial pressures and small concentration of water. Activation energies in the range 117 ± 8.4 KJ mol⁻¹ were obtained. After reaction, the mean Pd particle size obtained by electron microscopy decreased to one half of the initial value and diffraction patterns showed the presence of PdO. It is suggested that the reaction proceeds through the pitting mode over the carbon surface. A kinetic model is proposed to explain the results.     

CO3O4/MPS催化氧化NO性能

微乳法制备的介孔二氧化硅（MPS）负载Co3O4构成了Co3O4/MPS催化剂,考察了负载量、焙烧温度等制备条件和反应温度、空速、NO进口浓度、O2体积分数等操作条件对Co3O4/MPS催化氧化NO性能的影响,并对载体及催化剂进行了BET和XRD表征。结果表明：MPS比表面积远大于其它载体,Co3O4呈立方晶型,MPS负载25%的Co3O4在300 ℃下焙烧3 h得到催化剂的晶体颗粒最小,分散性好,具有最佳催化氧化活性和良好的稳定性,在NO进口浓度500 μL/L、O2体积分数10%、空速12 000 h－1的条件下,250 ℃时NO氧化率可达50%～60%（此时可获得最高的NOx吸收效率）,300 ℃氧化率达到80%以上,接近热力学平衡值。     

Catalytic activity of La-modified TiO2 for soot oxidation by O2

TiO₂ and La-doped TiO₂ samples with La loading between 0.2% and 2% have been prepared, characterised, and tested in the catalytic oxidation of soot by O₂. La doping prevents anatase to rutile phase transformation and crystallite size growth when heated at 800 °C, as deduced from XRD, Raman spectroscopy and BET surface area measurements. The optimum La loading was found to be 0.2%. The catalytic activity of TiO₂ and La-doped TiO₂ samples tested mainly depends on crystallite size, the lower the size the better the activity. TiO₂ phase composition is not a key factor in the catalytic oxidation of soot.     

Catalytic oxidation of NO over Ce-doped Mn/TiO2

Mn-Ce/TiO₂ catalyst was prepared by impregnating Mn-Ce on TiO₂ and was characterized by XRD,BET and PL. The influences of Ce-doping concentration,loading,calcinations temperature,space velocity,inlet concentration of NO and volume fraction of oxygen on the performance of catalytic oxidation were examined. The results showed that the effect of doping Ce not only increased the surface area of MnO_x/TiO₂ but also enhanced the dispersion of active phase over TiO₂. At Ce-doping concentration of [Ce]/[Mn]=1/3,10% loading Mn-Ce/TiO₂ catalyst calcined at 300 ℃ for 3 h had high catalytic oxidation activity. When inlet concentration of NO was 300 μL/L,O₂ 10%,space velocity was 41000 h^－1,oxidation rate of NO over Mn-Ce/TiO₂ reached 58% at 200 ℃.     

Cu掺杂Mn／TiO2催化氧化NO性能研究

采用溶胶凝胶法制备了栽体TiO2,在负栽Mn（Ac）：制备Mn／TiO2时掺杂cu,制备了Mn—Cu／TiO2催化剂。考虑了cu的掺杂量、活性组分负载量、焙烧温度等制备条件对其催化氧化No性能的影响。结果表明,最佳条件下制备的催化剂,在反应温度200℃、空速41000h～、No浓度为300×10-6（书）及O2含量为10％条件下,NO氧化率可迭53．08％,250℃时NO氧化率达到74．76％。在220℃以上时H2O对其影响较小,但其抗硫性能还有待进一步研究提高。     

Fe修饰Mn-Ce/Al2O3-TiO2催化剂对NO氧化性能的实验研究

采用溶胶凝胶法制备了TiO_2与Al_2O_3摩尔比为1∶4的Al_2O_3-TiO_2复合氧化物载体,使用共浸渍法制备了Mn,Ce质量分数分别为10%和2%的Mn-Ce/Al_2O_3-TiO_2催化剂,并通过添加不同质量分数的Fe对催化剂进行修饰。在固定床反应装置上进行了催化剂氧化性能的实验。结果表明:在空速为15 000 h~(-1),氧气体积分数为8%时,Fe的添加能够显著提升Mn-Ce/Al_2O_3-TiO_2催化剂的NO催化氧化性能,并在Fe质量分数为4%时,Mn-Ce-Fe(4)/Al_2O_3-TiO_2催化剂的NO催化氧化活性最优,280℃时NO的转化率达到86%。H_2-TPR实验结果显示,Fe的修饰使Mn-Ce/Al_2O_3-TiO_2催化剂的还原峰大幅向低温方向移动,改善了催化剂的氧化还原活性。     

抗坏血酸对Fe2+/H2O2体系氧化NO的促进作用

采用实验方法研究了低成本环境友好型添加剂抗坏血酸(AA)对Fe²⁺/H₂O₂体系氧化NO气体及其对体系内H₂O₂分解的影响,分析了AA对体系氧化NO能力及H₂O₂分解的影响机制。研究结果表明:AA通过加速Fe³⁺向Fe²⁺的转化而促进Fe²⁺/H₂O₂体系对NO的氧化。[AA]₀:[Fe²⁺]₀对体系氧化NO的能力及H₂O₂的分解具有重要影响。综合考虑NO氧化脱除量及H₂O₂消耗量,合理的[AA]₀:[Fe²⁺]₀为1/3~1/2。AA的分次添加方式可大幅度提升体系氧化NO气体的能力。研究结果可望为发展基于H₂O₂为氧化剂的烟气NO绿色氧化技术提供理论基础。     

V-MCM-41催化环己烯环氧化性能

采用水热法合成了V-MCM-41,并用ICP-AES、FTIR、DRS-UV-Vis、XRD、BET等技术对其进行了表征,发现只有部分V进入分子筛,所合成的V-MCM-41具有较高的结晶度,并且其结晶度随晶化液中V/Si摩尔比的增大而升高。V-MCM-41催化环己烯/H₂O₂氧化反应结果表明,当V-MCM-41中V含量大于1.10%（摩尔分数）时,骨架V-O-V物种在催化环己烯氧化反应的同时,也可加速H₂O₂的分解;乙腈是该反应体系的最佳溶剂,最佳反应温度为70℃。最佳反应结果表明,环己烯的单程转化率和H₂O₂有效利用率可分别达到23.91%和95.4%。     

Inhibition effect of carbon dioxide on the oxidation of hydrogen over a platinum foil catalyst

This paper investigates the catalytic ignition of the H₂/O₂/CO₂ mixture on platinum in a stagnation flow at atmospheric pressure experimentally and numerically. We measure the ignition temperatures of the gas mixtures flowing towards resistively heated platinum with various composition ratios and various diluent gases of N₂, Ar and CO₂. Compared with N₂ or Ar, the CO₂ dilution shows higher ignition temperature by about 50 K, even at the same composition ratio. The ignition temperature increase is proportional to the dilution ratio. Through the numerical simulation, it is illustrated that higher ignition temperature is caused by the adsorption of CO₂ and following dissociation on platinum surface, which was to date considered negligible in catalytic combustion.     

Catalytic oxidation of CO over ordered mesoporous platinum

Hexagonal phase mesoporous (H₁Pt) was recently reported to have different catalytic properties compared to conventional platinum catalysts. To further investigate this observation the catalytic activity of H₁Pt/Al₂O₃ for CO oxidation was compared with the activity of a corresponding catalyst prepared from Pt-black (Pt-black/Al₂O₃). The H₁Pt/Al₂O₃ catalyst showed ignition at lower temperatures but extinction at higher temperatures compared to Pt-black/Al₂O₃. These observations were further supported by oxygen step-response experiments at constant temperature, where the H₁Pt/Al₂O₃ catalyst showed ignition at lower oxygen concentrations when starting from a CO poisoned surface and extinction at higher O₂ concentrations when starting from the high-reactive state. Furthermore, adsorption of CO on the catalysts was studied in situ using infrared spectroscopy in absence and presence of oxygen after pre-oxidation and pre-reduction, respectively. At 150 °C the H₁Pt/Al₂O₃ sample showed activity for CO oxidation in the presence of oxygen regardless of pretreatment, whereas Pt-black/Al₂O₃ was inactive due to CO self-poisoning. The differences observed in the low reactive state are suggested to be due to structural differences of the platinum surface in the catalysts resulting in a lower sensitivity of the H₁Pt/Al₂O₃ catalyst towards CO self-poisoning and a higher capacity to activate oxygen, and thus a higher activity for CO oxidation. During the high reactive state, the observed higher sensitivity to the concentration ratio between CO and oxygen, and to the temperature is likely due to less optimal ratio between the sticking coefficients of the reactants on the H₁Pt catalyst and to higher mass-transport limitations in its narrower pores during the initial stage of the extinction.     

Catalytic wet-air oxidation of carboxylic acids on carbon-supported platinum catalysts

Catalytic wet-air oxidation (CWAO) of aqueous solutions (5 g · l⁻¹) of car☐ylic acids (formic, oxalic, and maleic) was carried out with air at 293–463 K on carbon-supported platinum catalysts. Platinum was loaded on active charcoal by cationic exchange, then reduced under H₂. Homogeneous dispersions of 1–2 nm metal particles were obtained. CWAO reactions were performed at 1 or 15 bar air pressure in stirred, batch reactors. Total conversion of formic and oxalic acids into carbon dioxide was obtained under very mild conditions (air at atmospheric pressure, 326 K). The Pt/C catalyst was almost inactive for the oxidation of acetic acid but maleic acid was oxidized under moderate conditions (15 bar of air pressure, 405 K) which indicates that the degradation of this acid does not occur via acetic acid.     

The promotion of carbon monoxide oxidation by hydrogen on supported platinum catalyst

This paper reports the results of a study of the combined oxidation of hydrogen and carbon monoxide on a platinum diesel oxidation catalyst. Experimental results for the light-off curves obtained in a monolith supported catalyst are shown for different concentrations. The presence of hydrogen is shown to promote the oxidation of CO, with the largest effect shown for the first small addition of hydrogen, then a progressively decreasing effect as the hydrogen concentration is increased. The enhancement effect can be successfully simulated using a kinetic model in which the activation energy for the desorption of CO is decreased as a function of hydrogen adsorption. Hydrogen is allowed to adsorb on sites only accessible to hydrogen and not CO or oxygen.     

Catalytic oxidation of aqueous methyl and dimethylamines by activated carbon

The catalytic wet air oxidation (CWAO) of methyl and dimethylamines was studied. A commercial peach stones activated carbon and its oxidized and reduced forms were used as catalysts. The observed catalytic behavior is related to the presence of oxygenated surface functional groups on the activated carbons. The N-compounds were selectively oxidized to nitrogen, water and carbon dioxide using these activated carbon catalysts. It is proposed that the quinonic surface groups are responsible for the selective catalytic oxidation of these amines. Carboxylic, lactonic and anhydride groups strongly adsorb the amine compounds producing inhibition of the catalytic activity of the activated carbon in the CWAO process.     

Fe2+/H2O2体系内各种自由基在氧化NO中的作用

Fe²⁺/H₂O₂体系可分解产生多种氧化性自由基, 主要包括O₂^-·、·OH和HO₂·。本文实验研究了O₂^-·、·OH及HO₂·在Fe²⁺/H₂O₂体系氧化NO气体过程中的作用。结果表明:在本实验条件下, O₂^-·对NO气体的氧化作用不明显;·OH及HO₂·是该体系氧化NO气体的主要活性物质, 其中·OH的氧化作用更大。加快自由基的生成速率可以增强Fe²⁺/H₂O₂体系对NO气体的氧化能力, 但O₂的生成速率同时加快。只有少量·OH及HO₂·参与NO的氧化, ·OH与HO₂·之间的快速反应是Fe²⁺/H₂O₂体系氧化NO过程中H₂O₂利用率低的主要原因。     

介孔Fe2O3/SBA-15催化臭氧氧化含酚废水

含酚废水来源广泛自然条件下难以去除,酚类物质毒性大对生态环境和人类生活健康造成了较严重的影响。本文选取了有机废水处理中较为高效的臭氧催化氧化技术,使用臭氧氧源曝气产生大量的含氧自由基,催化氧化降解酚类有机物,同时对活性中心载体进行了优化,选取制备了一类水热稳定性好及机械强度高的多孔材料,使用这些多孔材料对活性中心Fe₂O₃进行了再组装,合成了一系列表面富集Fe₂O₃的SBA-15介孔薄膜材料,由于SBA-15材料较大的比表面积、丰富的孔隙结构、高度分散的活性中心,在臭氧催化氧化含酚废水中取得了较好效果。苯酚溶液初始浓度为100mg/L (COD 238mg/L)、Fe₂O₃(5)/SBA-15催化剂投加量为30g、臭氧气体流量为2mg/min、废水HRT为5min、流量为0.8L/h的条件下,该催化剂能高效连续稳定运行500h不易失活,其COD去除率仍能保持在65%以上,催化剂活性依然保持在83%以上。Fe₂O₃/SBA-15类介孔催化材料在深度处理含酚废水中具有工业化应用潜质。     

Global kinetic models for the oxidation of NO on platinum under lean conditions

Different global kinetics for the oxidation of NO on platinum are compared in this work. The general form of the equation for the reaction rate is with . Furthermore steady-state and temperature-programmed experiments were performed. The best results of simulation coupled with parameter estimation were obtained using α = 0.28, β = 0.49, γ = 0 and δ = 1, along with an activation energy of 47.5 kJ mol⁻¹.