La-Na-Co-Mn-O系钙钛矿型催化剂同时去除柴油机碳颗粒和NOx性能的研究

采用低温燃烧法制备了Na+部分取代La3+的La1-xNaxCo0.5Mn0.5O3系钙钛矿型复合氧化物催化剂。利用程序升温反应(TPR)技术,对催化剂应用于柴油机常规排放物中的碳微粒(soot)和氮氧化合物(NOx)的同时催化脱除性能进行了研究。     

由贵金属取代的钙钛矿催化剂对碳烟的催化性能

用柠檬酸法制备了不同贵金属取代的钙钛矿LaCo0.96X0.04O3(X为Pt、Pd、Rh、Au、Ag)催化剂,用热重法测试了催化剂对碳烟的催化活性,采用程序升温还原法(H2-TPR)、X-射线衍射仪(XRD)、能量谱仪(EDS)和红外光谱(FTIR)对催化剂进行了测试.结果表明,催化剂LaCo0.96Ag0.04O3催化活性最高,起燃温度为449℃,远低于LaCoO3的504℃;各贵金属取代的钙钛矿LaCoO3的TPR还原峰变化各异;XRD特征峰的衍射角向高角度偏移,说明各贵金属进入了钙钛矿结构相;能谱图显示各贵金属进入钙钛矿相的量不同.     

催化技术去除柴油机排放碳颗粒的研究进展

综述了柴油机排放碳颗粒催化燃烧中运用的贵金属催化剂、过渡金属催化剂、(类)钙钛矿催化剂以及催化技术与低温等离子体技术协同作用的最新研究进展,介绍了上述催化剂和催化技术的作用机理,并探讨了它们在实际应用中存在的问题和应用前景。     

复合氧化物催化材料上碳颗粒物的催化燃烧

针对柴油车排放碳颗粒物的控制 ,研制可应用于柴油车排放碳颗粒物催化再生复合氧化物催化材料 .通过运用热分析仪 (TGA)和程序升温氧化反应装置 (TPO)对复合氧化物催化材料的活性进行评价 ,研究了催化材料的组成、原子配比、催化材料与碳颗粒物质量比、H₂O的加入、焙烧温度对催化活性的影响 .实验结果表明 :双组分金属氧化物催化剂中 ,Cu-Mo-O有较好的活性 ;多组分金属氧化物催化剂中 ,Cu-K-Mo-O在原子比Cu∶K∶Mo =1∶1∶2 ,催化剂与碳颗粒物质量比为 5∶1时活性最好 ,其碳颗粒物起燃温度为 32.7℃ ,同时H₂O和焙烧温度对该催化剂的影响较小 ,是能够应用于柴油车排放碳颗粒物控制催化再生的良好催化材料 .     

柴油车排气净化技术探讨

柴油车的排气污染受到了越来越多的关注。文章分别介绍了柴油机排气中氮氧化物的还原、碳烟颗粒物的氧化以及同时去除氮氧化物和颗粒物的各种催化净化技术及其最新研究进展,并对该研究方向存在的主要问题和应用前景进行了探讨。     

Preparation methods and thermal stability of Ba-Mn-Ce oxide catalyst for NOx-assisted soot oxidation

Manganese oxide-loaded and -doped ceria as well as the corresponding barium-modified oxide catalysts were prepared for soot oxidation in the presence of NOx, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller and NO temperatureprogrammed oxidation measurements. The activity of catalyst depended strongly on the NO2 production capacity, and the importance of surface nitrates was weakened without heat transfer limitations. The formation of perovskite-type oxides after the high-temperature calcination caused the loss of NOx storage capacity for the Ba-modified catalysts, but did not seem to affect the NO oxidation activity obviously. The addition of barium did not prevent the phase separation of MnOx-CeO2 solid solutions, whereas it inhibited the sintering of oxide crystallites effectively. This, as well as the relatively high surface area, resulted in a small increase in soot oxidation temperature for the thermally aged Ba/Mn-Ce catalyst.     

A novel four-way combining catalysts for simultaneous removal of exhaust pollutants from diesel engine

A novel four-way combining catalysts containing double layers was applied to simultaneously remove four kinds of exhaust pollutants(NOx,CO,HC and PM) emitted from diesel engine.The four-way catalysts were characterized using scanning electron microscope(SEM) and Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS).Their catalytic performances were evaluated by temperature-programmed reaction technology.The double layer catalysts could effectively remove the four main pollutants.The highest catalytic activity was given by the two-layered catalysts of La0.6K0.4CoO3/Al2O3 and W/HZSM-5.Under the simulated exhaust gases conditions,the peak temperature of the soot combustion was 421°C,the maximal conversion of NO to N2 was 74%,the temperature of the HC total conversion was 357°C,and the maximum conversion ratio of CO was 99%.     

La1-xKxMnO3催化剂同时消除柴油机尾气中NO和碳烟性能

采用溶剂热法制备La_1-xK_xMnO₃(x=0, 0.10, 0.15, 0.20, 0.25)钙钛矿型复合金属氧化物催化剂;通过XRD、FT-IR、SEM、H₂-TPR、XPS、NO-TPD等手段对催化剂的物相组成、表面形貌、氧化还原性能等进行了表征;在常压固定床微型反应装置中评价催化剂同时消除NO和碳烟催化性能.结果表明,制备的La_1-xK_xMnO₃催化剂均具有钙钛矿结构;K部分取代La-Mn钙钛矿结构中La后,颗粒结构得以改善,部分Mn³⁺价态升高为Mn⁴⁺,形成较多氧空位和Mn⁴⁺,提高氧化还原性能和吸附NO性能.活性评价结果表明,La_0.80K_0.20MnO₃催化剂表现出较好的同时消除NO和碳烟催化性能,NO最大转化率(Xmax NO)和对应反应温度(Tmax NO)分别为46.5%和436℃,碳烟起燃温度(T_ig)、CO₂浓度峰值温度(Tmax CO₂)和生成CO₂选择性(Smax CO₂)分别为341℃、454℃和98.8%.     

柴油车用NH_3选择性催化还原NO_x技术发展现状

文章介绍了NH3选择性催化还原NOx技术(SCR)的基本原理,主要讨论了TiO2和分子筛型催化剂的优缺点,以及这两种催化剂应用于柴油车尾气NOx净化的主要问题和相应的解决措施,为开发车用SCR催化剂提供必要的支持。     

SO2气氛下Cu-Ce-O催化剂氧化柴油车排气碳烟的性能

运用程序升温氧化(TPO)对共沉淀法合成的Cu-Ce-O催化剂进行了活性评价,考察了在不同浓度的S0,气氛下cu-Ce-O催化剂氧化模拟碳黑的性能,并用BET、XRD、TPR和FT-IR对催化剂进行了表征.BET和XRD测试显示,cu和ce的结合使催化剂比表面积增大,晶体结构发生变化,形成了复合氧化物;TPO活性测试结果表明,Cu-Ce-O复合催化剂比单一组分的CuO或CeO2具有更好的低温催化活性.复合氧化物cu-Ce-O中Cu原子含量越高,对应硫化后的催化剂氧化碳烟的能力越低,同时催化剂表面生成的硫酸盐越多,即催化剂抗硫中毒能力也降低.浓度低于0.03%的SO2对Cu-Ce-O的催化性能有一定的促进作用,但SO2的体积分数超过0.03%后碳黑燃烧速率变慢;FT-IR初步证实了高体积分数的SO2所产生的大量SO24-可能是抑制催化剂活性的原因.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems(Cu Cr2O4, Cu Co2O4), deposited onto cordierite monoliths of honeycomb structure with a second support(finely dispersed Al2O3), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine’s gas exhausts(O2, NOx, H2 O, CO2) and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series: O3 NO2> H2 O > NO > O2> CO2. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O3 occurs intensively(in the presence of copper chromite based catalyst) even at closing to ambient temperatures.Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Catalytic evaluation of promoted CeO2-ZrO2 by transition, alkali, and alkaline-earth metal oxides for diesel soot oxidation

Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr （χ= 0, 5, 10, 20）, they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation （TPO） in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270℃, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40℃ under loose contact condition.     

过渡金属-铈复合氧化物对碳烟的催化燃烧性能和表征

采用共沉淀法制备了不同过渡金属(Fe、V、Mn、Co、Cu)和铈的复合体氧化物催化剂,并用程序升温还原法(H2-TPR)、BET、XRD、拉曼光谱(RS)和光电子能谱(XPS)对催化剂进行了表征.同时,利用热重法测试了催化剂对碳烟的催化活性.实验结果表明,过渡金属的添加极大地提高了氧化铈的催化活性,其中,铈铁复合氧化物的催化活性最高.催化剂催化燃烧碳烟的活性与催化剂表面的耗氢量以及催化剂表面氧种OⅡ的含量紧密相关.     

V2O5/TiO2与MoO3/TiO2催化剂表面结构形貌及其对催化氧化碳烟活性的影响

为研究纳米级V₂O₅与MoO₃催化剂表面结构对其催化氧化碳烟活性的影响,以TiO₂为载体,采用等体积浸渍法制备了不同负载率(5%、10%、20%、40%)的V₂O₅/TiO₂与MoO₃/TiO₂催化剂,通过扫描电镜(SEM)、X射线衍射仪(XRD)对比研究了2种催化剂在TiO₂载体上的分散状态及物相结构.以Printex-U碳黑为试验用碳烟,采用热重分析仪对V₂O₅与MoO₃催化剂催化碳烟氧化的活性进行了比较.结果表明:V₂O₅与MoO₃在TiO₂载体上均存在一个单层分散饱和阈值,分别为V20(负载率为20%,下同)、Mo10,在该阈值前后活性组分在载体上分别以单层分散状态和明显的晶态存在.对于V₂O₅催化剂,其最佳催化活性出现在负载率接近单层分散饱和阈值时,与无催化状态相比,T_i(起燃温度)、T_p(最大失重率温度)以及T_f(燃尽温度)分别下降了69.1、46.0、23.0 ℃,有明显的阈值效应.而对于MoO₃催化剂,因其自身低熔点性而表现出良好的表面迁移能力,再加上α-MoO₃晶体特有的层状结构,使其可释放出更多的晶格氧,随着负载率的增加,该催化剂催化氧化碳烟活性持续增加,并且未观察到明显的阈值效应.研究显示,在相同负载率下,MoO₃催化剂催化氧化碳烟活性均高于V₂O₅催化剂.      

Combination of biodiesel-ethanol-diesel fuel blend and SCR catalyst assembly to reduce emissions from a heavy-duty diesel engine

In this study, the efforts to reduce NOx and particulate matter （PM） emissions from a diesel engine using both ethanol-selective catalytic reduction （SCR） of NOx over an Ag/Al2O3 catalyst and a biodiesel-ethanol-diesel fuel blend （BE-diesel） on an engine bench test are discussed. Compared with diesel fuel, use of BE-diesel increased PM emissions by 14% due to the increase in the soluble organic fraction （SOF） of PM, but it greatly reduced the Bosch smoke number by 60%-80% according to the results from 13-mode test of European Stationary Cycle （ESC） test. The SCR catalyst was effective in NOx reduction by ethanol, and the NOx conversion was approximately 73%. Total hydrocarbons （THC） and CO emissions increased significantly during the SCR of NOx process. Two diesel oxidation catalyst （DOC） assemblies were used after Ag/Al2O3 converter to remove CO and HC. Different oxidation catalyst showed opposite effect on PM emission. The PM composition analysis revealed that the net effect of oxidation catalyst on total PM was an integrative effect on SOF reduction and sulfate formation of PM. The engine bench test results indicated that the combination of BE-diesel and a SCR catalyst assembly could provide benefits for NOx and PM emissions control even without using diesel particle filters （DPFs）.     

铁锰轻稀土复合氧化物催化剂对苯的完全氧化作用

研究铁轻稀土，铁锰轻稀土复合氧化物催化剂对苯的催化活性，发现铁锰轻稀土复合氧化物催化剂对苯具有较理想的完全氧化活性；同时还研究了稀土用量及添加微量贵金属钯对催化剂性能的影响，发现轻稀土有一个恰当的添加比例，另外还发现添加微量钯可提高催化剂的初活性。     

钙钛矿型烯土复合氧化物及其在汽车尾气净化工程中的应用

本文介绍了钙铁矿型烯土复合氧化物的结构特征、制备方法与催化性能；分析了该类氧化物对汽车尾气环境的适应性，并与现有的贵金属催化剂作了比较．     

金属氧化物催化剂上吡啶催化燃烧

为了研究催化燃烧法净化挥发性有污染物的可能性,考察了金属氧化物催化剂上吡啶的氧化活性及氧化过程ＮＯｘ控制能力,吡啶氧化产物ＮＯｘ随反应温度升高呈现极大值。催化剂的氧化活性ＮＯｘ控制能力呈正比关系。     

Cu-K型低温碳烟氧化催化剂的合成及表征

柴油机排放中碳烟的低温氧化是近年来研究的热点.通过原位合成法制备Cu2K/Al2O3和CuK／Al2O3两种碳烟氧化催化剂,并采用低温氮吸附/脱附实验、X射线衍射、X射线光电子能谱、程序升温氧化对其结构进行系统表征,并用U碳模拟柴油机碳烟,研究其催化活性,评测其对柴油机排气中碳烟颗粒的净化效果.研究表明,Cu2K/Al...     

La-M-Co-O/堇青石催化剂的制备及催化氧化氯苯

采用柠檬酸络合法制备La-M-Co-O（M=Mn,Cr,Fe,Ni和Cu）/堇青石催化剂,运用BET,XRD,SEM,H₂-TPR和XPS技术对催化剂性能及微观结构进行表征分析,研究考察过渡金属掺杂,掺杂量以及焙烧温度等对催化剂催化氧化性能的影响.结果表明,随着催化剂焙烧温度升高至650℃时,催化剂表面所负载的活性氧化物颗粒最为分散,其氧化活性最佳,且当反应温度为350℃时,催化剂催化氧化氯苯转化率可达96.4%,究其原因是高温焙烧致使催化剂形成LaCoO₃钙钛矿型复合氧化物,其复合氧化物的晶体结构有利于催化剂催化氧化氯苯性能的提高.