车用三元催化转化器的化学反应机理研究

在简要介绍三元催化转化器工作过程的基础上，论述和比较了转化器中的几种化学反应机理，分析和研究了各个机理的长处和不足及其内在规律，使之能根据模拟精度选择相应的反应机理，具有参考价值。     

4108型柴油机排气三元催化转化试验研究

通过KD2型三元催化转化器应用于41087ZLQ型增压中冷柴油机的发动机台架试验,分析了三元催化转化器对此类型柴油机动力性、经济性和排放的影响.试验结果表明,三元催化转化器的应用对此类型柴油机的动力性和经济性无较大的影响;可以显著降低CO、HC的排放,而对降低NOx的排放效果却不明显.为了得到更好的净化效果,需要采用机内和机外综合净化措施,即在使用三元催化转化器的同时,增加EGR系统、微粒过滤器等.     

基于AMESim的三元催化转化器起燃特性数值模拟与优化设计

为研究三元催化转化器（TWC）的起燃特性,采用AMESim软件建立了某车型三元催化转化器的物理模型,用数值求解气固两相的质量守恒和能量守恒方程组的方法对其进行了模拟计算,并得到了不同影响因数下的CO,NOx、CaHb等废气转化率曲线。结果表明,三元催化转化器的位置及其内部结构对起燃特性都有影响。     

三元催化转化器的使用及对发动机的影响

介绍汽车用三元催化转化器、氧传感器的结构性能和工作原理，阐述正确的使用方法及对发动机的影响，有利于环境保护措施的贯彻落实。     

补气装置及其位置对三元催化转化器转化效果的影响

本文主要介绍在汽油机与三元论转化器之间两个不同位置安装自动补气试验研究的装置,方法和结果,并给出了补气装置处于不同位置时,发动机废气中反映三元催化转化器转化效果的ＨＣ,ＣＯ和ＮＯ含量,据此可对自动补气装置的最佳位置进行分析。     

汽油机油对汽油车三元催化器中毒老化的影响

利用汽油燃烧器老化系统,采用低温机油中毒老化试验循环考察了汽油机油中的磷的质量分数、硫酸盐灰分和二烷基二硫代磷酸锌(ZDDP)类型对汽油车三元催化转化器中毒老化的影响.结果表明:汽油机油中的磷可引起三元催化器中毒,导致三元催化器对汽油车排放污染物(CO、THC和NOx)的起燃温度升高、转化效率降低;硫酸盐灰分可以延缓三元催化器的磷中毒;相同磷的质量分数条件下,仲烷基ZDDP(T205)相比伯烷基ZDDP(T202)对三元催化器的中毒影响更大.     

汽油机车辆尾气排放控制技术发展现状

本文从机内净化和机外净化两个方面阐述了汽车尾气排放控制技术和发展现状 ,着重介绍了电子控制、可变气门正时和升程、可变进气管长度、三元催化转化器、废气再循环系统等尾气净化措施 ,以及提高燃油品质在尾气排放控制中的重要性     

排气的进一步净化

排气的进一步净化根据Ｒｉｃｈａｒｄｏ动力系统研究部门的Ｏ－ｍａｒＨａｄｄｅｄ的观点，要满足１９９７年出台的Ｅｒｕｏ２排放法规就需要有一种比当前用于车用汽油机的三元催化转化器更好的排气控制系统。而且，由于欧洲试验循环及Ｅｕｒｏ３法规将涉及冷却起动时的排...     

4GE型汽油机三元催化转化试验研究

通过对采用闭环多点电控喷射系统并装用三元催化转化器的4GE型汽油机的试验证明,其排放值完全符合排放法规要求,对噪声影响不大,功率损失很小且对有害物的转化率很高,取得了满意的排放效果。     

汽油机车辆尾气排放控制技术发展现状

本文从机内净化和机外净化两个方面阐述了汽车尾气排放控制技术和发展现状,着重介绍了电子控制、可变气门正时和升程、可变进气管长度、三元催化转化器、废气再循环系统等尾气净化措施,以及提高燃油品质在尾气排放控制中的重要性.     

The used automobile catalytic converter as an efficient catalyst for removal of malathion through wet air oxidation process

The automobile catalytic converter (ACC) contains a huge number of precious metals as catalysts. When an ACC fails to meet standards, it is removed from the exhaust of an automobile but retains some catalytic activity. However, the recovery and/or activation of this waste is a high-cost process and includes several chemical treatments. Catalytic wet air oxidation (CWAO) has been reported as an effective wastewater treatment method. The most important disadvantage of CWAO is cost-nonefficiency. Herein, to overcome these problems, the simple recovery of catalysts from waste ACC for reuse in CWAO was investigated. The optimum conditions of reaction were investigated through response surface methodology (RSM). The optimum removal efficiency was 88% when the reaction conditions were set on the 20 bar of pressure at 111.5 °C over 77 min and using 0.41 g of recovered catalyst. In addition, toxicity testing was performed on a model of malathion-contaminated wastewater before and after CWAO treatment. Final product identification was performed which showed that CWAO eliminated the toxicity of wastewater and was determined to be malaoxon, present at acceptable concentrations, and tributyl phosphate. In conclusion, there may be important potential for the use of recovered ACC catalyst in the treatment of toxic wastewater.     

The role of oxygen vacancies in the CO2 methanation employing Ni/ZrO2 doped with Ca

The Ni/ZrO₂ catalyst doped with Ca and Ni/ZrO₂ were employed in the CO₂ methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO₂ and chemical analysis. The catalytic behavior of these catalysts in the CO₂ methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO₂, the metallic surface area did not change whereas the CO₂ consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca⁺² but also some Ni²⁺ are on the ZrO₂ surface lattice of the Ni/CaZrO₂ catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO₂ methanation rate increases. Moreover, the number of active sites of the CO₂ methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs.     

Effect of gas-phase reaction on catalytic reaction for H2/O2 mixture in micro combustor

The catalytic reaction characteristics of the hydrogen and oxygen mixture in the catalytic micro-combustor were detected by thermocouple, infrared thermal imager and OH-PLIF. The equivalence ratio of transition stage from coupling reaction (coupled homogeneous-heterogeneous combustion) to pure catalytic reaction (heterogeneous combustion) was obtained. The three-dimensional pure catalytic reaction model with detailed catalytic reaction mechanism was established in a rectangular catalytic micro-combustor. The simulation model was validated with experimental data. The effects of the intermediate and final products from gas-phase reactions on the pure catalytic reaction were discussed as well as the effects of gas-phase reactions on the catalytic reaction in the process of coupling reactions were studied. The intermediate product OH radical can improve the hydrogen conversion of the surface reaction, and the effect of O radical is not obvious. The final product H₂O has an inhibitory effect on the surface reaction. Since the mass fraction of H₂O is much higher than other gas-phase reaction products, the dominant effect of the gas-phase reaction on the catalytic reaction is suppression. In the coupling reactions, the fuel consumed by the gas-phase reaction weakened the catalytic reaction.     

CuCo2O4–NiO heterostructure catalysts for hydrogen production from ammonia borane

Ammonia borane (NH₃BH₃, AB) has been considered as one of the most attractive candidates for chemical hydrogen-storage materials and chemical hydrogen generation materials. Development of low-cost and high-performance catalysts for hydrogen generation from AB is highly desirable, which is still a huge challenge. Hollow sphere CuCo₂O₄ promotes the catalytic hydrolysis of AB due to its unique hollow sphere shape and the synergistic effect of Co and Cu elements. In this study, a heterogeneous structured catalyst containing NiO and CuCo₂O₄ was developed by a simple and low-cost method in order to improve the catalytic performance of CuCo₂O₄. Initially, CuCo₂O₄ with hollow sphere structure was synthesized by hydrothermal method, and then NiO were deposited onto CuCo₂O₄ by impregnation-calcination method to form a heterogeneous structure. The CuCo₂O₄–NiO catalyst showed good catalytic activity for the hydrolysis of AB. The catalytic performance of CuCo₂O₄–NiO was then optimised by controlling the concentration of the impregnated salt solution, and the optimised catalytic performance was 1.42 times that of pure CuCo₂O₄ with a HER value of 870 mL_H2g_cat⁻¹min⁻¹. This low-cost CuCo₂O₄–NiO obtained by impregnation-calcination method is valuable for catalytic hydrogen production from AB.     

催化燃烧对HCCI发动机着火点、燃烧性能及排放的影响

对甲烷在催化剂铑(Rh)表面的反应机理进行了分析。通过修改CHEMKIN软件包中的SENKIN模块,对活塞顶涂有催化剂的HCCI发动机的燃烧过程进行了数值计算,建立了单区、多区模型。利用单区模型分析了催化燃烧对HCCI发动机着火时刻的影响,结果表明在控制HCCI发动机着火时刻方面催化燃烧有其他方式所没有的优势;利用多区模型分析了催化燃烧对HCCI发动机的燃烧性能及HC、CO、NOx排放的影响,结果表明催化燃烧对燃烧效率、着火持续期有较大的影响,同时能降低HC、CO的排放,但会提高NOx的排放。     

Numerical studies of catalytic combustion in a catalytically stabilized combustor

This work aims to investigate numerically the catalytic combustion of a catalytically stabilized combustor. The numerical model treated a catalytic channel deposited with Pt and used a plug model of laminar, one‐dimensional, and steady‐state flow. The predicted conversions of mixture and ignition temperatures of surface reaction agreed well with the measured data when a multi‐step mechanism was used for the CH₄ surface reaction over Pt. The flame speed of a mixture supported by catalytic surface reaction was found to increase compared with a mixture without a catalytic combustion. CO mole fractions were analysed for three cases—gas reaction, surface reaction, and gas reaction coupled with surface reaction. The case of solely gas reaction produced the most CO emission and the case of solely surface reaction generated the least CO emission. The position where flame ignites was also evaluated numerically. There was only a small difference between the measured and predicted results on the starting points of flame in the catalytic channel. As a result, the plug model was shown to model surface ignition very well, however, it did not predict well the position of flame ignition. Copyright © 2000 John Wiley & Sons, Ltd.     

Enhancing resistance of carbon deposition and reaction stability over nickel loaded fibrous silica-alumina (Ni/FSA) for dry reforming of methane

Syngas production from the dry reforming of methane is now the most extensively utilized method for removing massive amounts of greenhouse emissions. Effective solutions towards the utilization of greenhouse gases such as CO₂ and CH₄ are scarce, except for power generation in the energy sector, which is a major source of CO₂. Herein, dry reforming of methane was experimented for the first time using an effective catalytic system composed of 5% Ni fibrous silica-alumina (FSA) that was successfully fabricated using a hydrothermal method. The characterization results from XRD, FESEM mapping, TEM, BET,XRF, FTIR, H₂-TPR, TGA/DTA, and Raman spectra demonstrated that Ni/FSA is composed of orderly Ni dispersion, small particles of Ni, robust basic sites, and high oxygen vacancies which enhanced the catalytic efficiency. The synthesized Ni/FSA also reduced coke formation and had long-term stability with no evidence of inactivation during and after the catalytic cycles. The superior activity of Ni/FSA was manifested in the high conversion rates of CH₄ and CO₂ at 97% and 92% respectively, with a H₂:CO ratio of ≈ 1. The stability of Ni/FSA was also sustained over 30 h of operation at 800 °C. The findings of the Raman, TEM, and TGA/DTA tests revealed that the spent Ni/FSA catalysts did not exhibit graphitic carbon or metal sintering in significant amounts when compared to commercial Ni–Si/Al catalysts.     

表面催化反应对小尺度空间内气相燃烧的影响

表面催化燃烧是微、小尺度空间内组织燃烧的重要手段.采用表面催化反应动力学方法,基于FLUENT软件自主开发了仿效CHEMKIN的催化反应动力学模型,实现了化学反应和流动的同步模拟.通过验证算例发现,该模型可获得与DETCHEM软件一致的计算结果,且与实验结果符合较好.采用该数值模型,对小尺度二维渐扩通道内Pt表面催化时CH4/空气燃烧进行研究.计算结果表明,不同当量比时表面催化反应都显著缩小了气相燃烧的熄火距离;气相燃烧火焰面增厚,火焰前沿处温度梯度变小.此外,表面催化对贫燃料燃烧的影响更显著.     

基于模型的三元催化转化器故障诊断方法研究

催化器性能是车载诊断(on board diagnostics,OBD)系统必须监测的项目之一。根据催化器的储、放氧特性,分析催化器储、放氧的主要工作过程。根据双线性氧传感器信号,建立催化器的储、放氧模型,同时引入催化器的存储、释放氧气能力指数参数、催化器氧容量OSC、催化器存储、释放氧气速率μ等指标来对催化器性能进行评估。通过"浓稀法"试验,采用最小二乘法对模型的参数进行辨识。根据辨识结果,利用模型仿真对催化器性能参数进行估计,同时引入催化器老化因子ρ。研究结果表明:在催化器不同老化程度(ρ=1、0.8、0.6)下,催化器性能指标(、OSC、μ)均下降,能够有效反映催化器性能的变化,可用于催化器性能的在线估计。     

Proposal for effective stacking method of structured catalyst

In this study, a micro–partition (MP), structure with micro–scale fins and holes made of aluminum was stacked as a structured catalyst. The effect of this stacking on the reactivity of a methanol steam reforming reaction was examined. The reactivity was improved by promoting the fluid mixing effect in the reactor by the stacking of the characteristic MP structure. However, the reactivity was reduced when the number of MP catalysts (MPCs) to be stacked was increased and packed densely. Moreover, it was suggested that the reactivity could be improved by investigating the factors of the effective stacking method for a catalytic reaction. We proposed the MPC stacking method in terms of the number, position, distance, and orientation of MPCs, such that the fluid mixing effect was promoted and MPC worked uniformly, based on a numerical simulation. The effect of the proposed stacking method on the reactivity was experimentally demonstrated.