氧化铝改性高铈铈锆复合氧化物的制备及其负载钯催化性能

通过共沉淀法制备高比表面积、高孔容的氧化铝改性高铈铈锆复合氧化物,并研究氧化铝改性、前驱体含水焙烧等因素对铈锆复合氧化物结构及负载钯催化性能的影响。研究结果表明:氧化铝改性能够大幅度提升高铈铈锆复合氧化物的比表面积、孔容和高温稳定性。改性样品的新鲜比表面积为122.01 m^(2)/g,孔容为0.4750 mL/g;经1000℃、4 h高温老化后样品的比表面积为66.28 m^(2)/g。前驱体含水焙烧可以提高氧化铝改性铈锆复合氧化物的储氧能力,增强铈锆复合氧化物的高温稳定性;焙烧样品经1000℃、4 h高温老化后的比表面积比常规铈锆复合氧化物提高2.28 m^(2)/g,比常规铈锆铝复合氧化物提高2.75 m^(2)/g。此外,氧化铝改性还可以增大新鲜负载Pd催化剂的空燃比窗口,对催化剂的C_(3)H_(8)、NO催化性能具有促进作用;而前驱体含水焙烧对老化态氧化铝改性负载Pd催化剂的CO、C_(3)H_(8)、NO催化性能均有明显促进作用。

Synthesis of La-hexaaluminate catalyst for methane combustion by a reverse SDS microemulsion

La-hexaaluminate catalyst for methane catalytic combustion was synthesized by a reverse microemulsion. Pseudo-temary phase diagrams of a quaternary microemulsion system of sodium dodecyl sulfate （SDS）, n-pentanol, n-octane, and water （or Al（NO3）3 solution） were presented. The effects of alcohol chain length, cosurfactant-to-surfaqtant rat!0, and salt concentration on the formation and stability of the microemul- sion system were studied. The phenomenon that the conductivity changed with water supported the phase behavior of the microemulsion system. La（MnffFex）Al12_xO19_a catalysts, applied in methane combustion and with high-temperature stability, were synthesized within the stable areas of the phase diagram of the microemulsion system, when SDS was chosen as surfactant, n-pentanol as cosurfactant, and n-octane as oil phase. The physical properties and structure of the catalysts were characterized by BET method, transmission electron microscope （TEM）, and X-ray diffraction （XRD）. A micro-fixed-bed reactor was used to measure the catalytic activity of hexaaluminates in methane combustion. The results show that the reverse microemulsions can be used to produce discrete La-hexaaluminate nanoparticles that display excellent methane combustion activity owing to their high surface area and high thermal stability.

汽车尾气催化剂贵金属含量手持XRF检测技术研究

汽车尾气催化剂可有效降低尾气排放,Pt、Pd、Rh贵金属是汽车尾气催化剂中的主要活性组分,贵金属含量在一定程度上决定着催化剂的活性、耐久性和使用寿命。贵金属含量检测对于汽车尾气催化剂的质量控制、市场监管以及废旧回收等十分重要。研究了手持X射线荧光(XRF)检测技术对陶瓷整体式汽车尾气催化剂、汽车尾气催化剂粉体、金属整体式摩托车尾气催化剂等样品进行贵金属含量测试。研究结果表明:与常规电感耦合等离子体发射光谱(ICP-OES)方法相比,手持XRF检测技术是一种较为可靠、快速、方便、廉价的贵金属含量测试方法,对于汽车尾气催化剂粉体,手持XRF检测与ICP-OES认证值对于Pd含量相对标准偏差小于±5%。XRF也可直接用于陶瓷整体式汽车催化剂或金属整体式摩托车催化剂的贵金属含量测试,XRF检测不仅能快速测试催化剂贵金属含量,而且可以获知贵金属种类、贵金属分布以及贵金属涂层涂覆工艺等信息。

Synthesis of hexaaluminate catalysts for methane combustion by reverse microemulsion medium

The aim of this study is to synthesize the catalysts of Fe- and Mn-substituted hexaaluminate by reverse microemulsion medium for methane catalytic combustion application. Pseudo-ternary phase diagrams in quaternary microemulsion systems of cetyltrimethylammonium bromide (CTAB), n-butanol, n-octane, and water [or Al(NO3)3 solution] were presented. The effects of the alcohol chain length, ratio of sur-factant to cosurfactant, and salt concentration on the formation and stability of microemulsion systems were studied. The phase behavior of microemulsion systems was confirmed through the varying of the conductivity with the water content. The performance and structure of the catalysts, La(Mn x /Fe x )Al12?x ? O19-δ synthesized with the optimal parameter in the phase diagrams of microemulsions systems were characterized by BET, TG-DTA, and XRD. The micro fix-bed reactor was used to measure the catalytic activities of catalysts to methane combustion. The results showed that this synthesis method could yield non-agglomerated and highly dispersed precursors that would undergo crystallization at the lower temperature of 950°C. When temperature was raised up to 1050°C, the complete crystalline La-hexaaluminate was shaped. The hexaaluminate substituted with Fe had high-catalytic activity and stability at high temperature, while the Mn-substituted had higher catalytic activity at lower temperature. When the cooperation of Fe and Mn occurred, i.e., LaFeMnAl10O19?δ exhibited a high surface area and catalytic activity to CH4 combustion, the CH4 light-off temperature was only 475°C and the complete combustion temperature was 660°C. This was attributed to the synergistic effect between Fe and Mn.

Catalytic activity of Mn-substituted barium hexaaluminates for methane combustion

The catalysts of hexaaluminate (BaMn x Al12?x O19?δ , x = 1.0, 2.0, 3.0, 4.0) to be used in methane combustion have been successfully synthesized by co-precipitation method and supercritical drying. The crystalline structure and surface area of catalyst were characterized by X-ray diffraction (XRD) and nitrogen adsorption analysis of BET method. BET analysis revealed that the preparing and drying method proposed here provides stable materials with higher surface area of 51.4 m2/g in comparison to materials prepared using conventional ambient drying method for BaMn x Al12?x O19?δ calcined at 1200° under oxygen. XRD analysis indicated that formation of a pure single phase BaMn x Al12?x O19?δ occurred up to x = 3 in the case of Mn-substituted barium hexaaluminates. Incorporation of Mn in excess leads to BaAl2O4 phase formation. As far as the valence state of Manganese ions was concerned, the introduced Mn ions were either divalent or trivalent. The first Mn ions were introduced in the matrix essentially as Mn2+ and only for BaMn3Al9O19?δ does manganese exist exclusively as Mn3+; the higher the Mn concentration, the higher the proportion of Mn3+. Catalytic activity for methane combustion has been measured for Mn-substituted barium hexaaluminates, light-off temperature was observed in the 512?624°C range. The highest activity was obtained for catalysts containing 3 Mn ions per unit cell, which reveals that the BaMn x Al12?x O19?δ catalyst was a promising methane combustion catalyst with high activity and good thermal stability. Temperature programmed reduction (TPR) under hydrogen has been used to correlate the catalytic activity with the amount of easily reducible species.