梅德清, 李显明, 赵翔, 袁银男. 钼基催化剂活性特征及其催化柴油机碳烟氧化特性[J]. 农业工程学报, 2014, 30(22): 30-36. DOI: doi:10.3969/j.issn.1002-6819.2014.22.004
    引用本文: 梅德清, 李显明, 赵翔, 袁银男. 钼基催化剂活性特征及其催化柴油机碳烟氧化特性[J]. 农业工程学报, 2014, 30(22): 30-36. DOI: doi:10.3969/j.issn.1002-6819.2014.22.004
    Mei Deqing, Li Xianming, Zhao Xiang, Yuan Yinnan. Surface activity structure of Mo-based catalyst and its characteristics of soot oxidation in diesel engine[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2014, 30(22): 30-36. DOI: doi:10.3969/j.issn.1002-6819.2014.22.004
    Citation: Mei Deqing, Li Xianming, Zhao Xiang, Yuan Yinnan. Surface activity structure of Mo-based catalyst and its characteristics of soot oxidation in diesel engine[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2014, 30(22): 30-36. DOI: doi:10.3969/j.issn.1002-6819.2014.22.004

    钼基催化剂活性特征及其催化柴油机碳烟氧化特性

    Surface activity structure of Mo-based catalyst and its characteristics of soot oxidation in diesel engine

    • 摘要: 为探究钼基催化剂的表面活性相结构,采用浸渍法制备了不同钼负载量纳米级MoO3/TiO2催化剂,通过比表面积分析仪(BET,brunner-emmet-teller)、傅里叶红外光谱分析(FT-IR,fourier transform infrared spectrometer)、X射线衍射仪(XRD,X-ray diffractomer)以及扫描电镜(SEM,scanning electron microscope)对催化剂的物化特性进行了表征。同时,为探究钼基催化剂改善碳烟催化氧化特性,以Printex-U碳黑作为实际发动机颗粒的替代物,利用热重分析法探究钼基催化剂对碳烟的催化氧化特性,并基于Starink法定量表征碳烟催化氧化反应过程。结果表明:较低钼负载量时,活性组分MoO3主要以非晶态或小晶态存在。当负载量超过10%时,催化剂表面开始出现正交晶系MoO3结晶区,所有样品均以稳定的钼氧双键形态存在在松接触状态下,具有低熔点性质的MoO3仍表现出良好的催化效果。随着MoO3/TiO2催化剂上钼负载量的增加,碳烟氧化特征温度随之降低,催化剂活性呈递增趋势,其并未受阈值效应与比表面积的制约,仅与活性组分MoO3含量呈正比关系。催化剂Mo∶Ti质量比为40∶60表现出最高的催化活性,与无催化剂状态相比,此时催化剂碳烟的起燃温度、峰值温度、燃尽温度分别降低了约84.4、122.6和122.7℃。Starink法热力学分析得到催化剂活性序列为无催化剂<Mo∶Ti(质量比为5∶95)<Mo∶Ti(质量比为10∶90)<Mo∶Ti(质量比为20∶80)<Mo∶Ti(质量比为40∶60)。因此,负载型钼基催化剂的催化活性随其质量负载量的增加而增加。

       

      Abstract: Abstract: The diesel particulate filter (DPF) with the trapping has become an effective and broadly used measure. However, the trapped particulates adhering to the carrier channel easily block the exhaust channel, and then consequently affect the power performance and fuel economy of the diesel engine. Catalytic technology can effectively reduce the temperature for soot combustion by coating the active catalytic material on the channel wall of DPF. The molybdenum catalyst shows excellent catalytic performance in many research fields. The high catalytic activity of molybdenum catalysts is mainly related to the mobility of the active species in the reaction condition, or by the surface migration or by the melting of molybdenum catalyst, so this mobility could improve the contact between reactants and catalyst. Thus, according to that idea, in a loose contact situation between soot and catalyst, the migration of the active component across the soot surface could play an important role in the oxidation reaction during trap regeneration. In order to thoroughly study the surface activity structure phase of the supported molybdenum catalyst and its' function mechanism on soot oxidation, nano-scale MoO3/TiO2 catalysts for soot oxidation were prepared by loading different amounts (5%, 10%, 20% and 40%) of MoO3 on the TiO2 particles through an impregnation method. The structures and physico-chemical properties for those catalysts were characterized using BET, Fourier transform infrared spectra (FT-IR), X-Ray diffraction (XRD) and a Scanning electron microscope (SEM). Printex-U carbon black has been often used in the research field of catalytic oxidation of diesel soot. The practical engine soot and Printex-U carbon black have more characteristics in common such as components and structures. Besides, the reproducibility of the test seemed satisfactory, too. Printex-U carbon black was chosen to replace the practical engine soot. The catalytic activity of molybdenum catalysts for soot oxidation was evaluated using a TG/DTA analyzer. Based on the Starink method, the catalytic oxidation process of soot was quantitatively analyzed. The results showed that, for the limitation of dispersion threshold value, the structure of active MoO3 was amorphous or micro crystalline at the low molybdenum loading. When the MoO3 loading rate was more than 10%, the significant MoO3 orthorhombic crystals appeared on the catalyst surface. The light sheet and octahedral crystal structure with close texture appeared in the MoO3 catalyst surface. The functional groups Mo=O were stable in all samples, and its content increased with the increase in molybdenum loading rate. Under a loose contact state, MoO3 characterized with low melting point, still showed good catalytic effect. With the increase in MoO3 loading rate, TG and DTG curve moved to the low temperature area, the characteristic temperatures of soot oxidation were decreased, and the catalytic activity of catalyst was increased. Conversely, the specific surface area and pore volume of the molybdenum catalyst were decreased. However, the catalytic activity was not limited by the specific surface area and threshold effect, and it was closely bound up with the content of the active component MoO3. Among all samples, the catalyst loaded by 40% MoO3 exhibited the highest catalytic activity for soot oxidation. The ignition temperature, the temperature of weight loss peak and the burnout temperature of soot oxidation were reduced about 84.4, 122.6 and 122.7℃ respectively, as compared with the non-catalyzed particulates. The order of the activation energy for soot oxidation worked out by the Starink method was soot < Mo:Ti (mass ratio 5:95) < Mo:Ti (mass ratio 10:90) < Mo:Ti (mass ratio 20:80) < Mo:Ti (mass ratio 40:60). Thereby, with the increase in the MoO3 loading rate, the catalytic activity of MoO3/TiO2 catalyst was increased.

       

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