有机废气催化燃烧用贵金属钯整体式催化剂的研究

催化燃烧法是当前处理挥发性有机废气最有前景的方法.贵金属钯催化剂对有机废气具有较高的催化燃烧活性,因此研究钯整体式催化剂用于有机废气的洁净化处理具有较好的工业应用前景.主要介绍了化学镀法制备贵金属钯整体式催化剂的基本原理、特点和制备工艺.     

化学镀制备Pd催化剂及在甲醛催化燃烧中的应用

为实现采用催化燃烧法对甲醛进行净化处理,采用化学镀法制备Pd-堇青石蜂窝陶瓷整体式催化剂,并对催化剂进行表征和活性评价。结果表明:化学镀法可以实现纳米Pd微晶颗粒在堇青石蜂窝陶瓷载体上均匀负载,焙烧后PdO与载体结合牢固,具有良好的抗振荡性和热稳定性;500℃焙烧的Pd-堇青石蜂窝陶瓷整体式催化剂的催化活性最高,在甲醛质量浓度为0.4~10 mg/m3,空速为1 500~6 000 h-1的条件下,催化剂具有良好的活性。     

Mo对贵金属Pd/Al-Ti整体式催化剂催化燃烧苯反应性能的影响

采用浸渍法制备了Mo掺杂的Pd/Al-Ti系整体式催化剂,考察了Mo添加量对Pd-Mo/Al-Ti整体式催化剂催化燃烧苯反应性能的影响,并对催化剂的稳定性做了研究。结果表明,Mo的添加明显提高了Pd/Al-Ti催化剂性能,当Mo添加量为5%时,催化活性最高,在225℃时苯转化率可达90%。采用X射线衍射、X射线光电子能谱、H2程序升温还原、NH3程序升温脱附和氮吸附等手段对催化剂进行表征,结果表明,Mo的加入增加了Pd物种在催化剂表面的分散,并调变了催化剂表面酸性、促进了催化剂表面氧浓度的增加,从而提高催化剂性能。研制的0.10%Pd-5%Mo/Al-Ti整体式催化剂在相同的反应条件下与0.25%Pd/Al-Ti整体式催化剂催化活性相当。     

贵金属催化剂低温催化氧化一氧化碳研究进展

随着“双碳”政策的不断推行以及人们环保意识的不断提高,一氧化碳(CO)作为典型的大气污染物,已成为工业废气和汽车尾气排放的主要控制对象。贵金属型CO氧化催化剂具有优异的低温活性、抗中毒抗性能,是CO催化氧化处理的最为有效的手段之一。基于贵金属型CO氧化催化剂的研究现状,重点围绕Pt、Pd、Au、Ag、Rh贵金属催化剂的贵金属调控技术和载体可控技术进行综述,总结了贵金属型CO氧化催化剂的性能优化策略和发展方向,为开发高性能的CO氧化催化剂提供指导。     

新型Pt基整体式催化剂的结构与催化性能

以堇青石蜂窝陶瓷(CHC)为载体,采用化学镀法制备Pt基整体式催化剂Pt-CHC,研究Pt-CHC催化剂在甲醛催化燃烧中的催化性能;对Pt-CHC催化剂在不同的甲醛初始浓度范围、较宽的空速范围与不同的进样相对湿度条件下进行活性测试,并进行扫描电镜和X射线能量色散谱表征。结果表明:Pt-CHC催化剂在Pt负载量较小(质量分数为0.24%)时,甲醛可在100℃时基本转化完全;活性组分Pt在蜂窝陶瓷载体表面选择性富集,Pt颗粒在催化剂中通孔道内部与孔口处均能基本维持均匀分布,颗粒粒径小于100 nm。     

堇青石蜂窝陶瓷载体酸处理对整体式La0.8Sr0.2MnO3催化剂催化甲苯燃烧性能的影响

整体式催化剂是一种常用的催化剂,蜂窝陶瓷载体是其重要组成部分。酸处理可以改进其结构上的不足。使用不同质量分数、种类的酸溶液对堇青石蜂窝陶瓷载体进行了预处理,考察了酸处理对整体式催化剂的基本性质及甲苯催化活性的影响,并采用XRD、BET等表征手段进行分析。结果表明,蜂窝陶瓷载体经质量分数为30%硝酸溶液处理后可达最佳效果,负载率提高48%以上,比表面积扩大20倍以上,由其制得的催化剂催化甲苯燃烧的起燃温度为219℃,降低了19℃,完全转化温度为281℃。表征结果说明酸洗过程未改变载体组成,而是使载体比表面积增加20倍以上,从而提高了整体催化剂的催化活性。     

催化剂对乙醇催化燃烧法制备碳纳米纤维的影响

分别以硝酸铁、硝酸钴、硝酸镍以及氯化铁、氯化钴、氯化镍作为催化剂先体，利用乙醇催化燃烧法制备了碳纳米纤维。利用扫描电子显微术、透射电子显微术和X射线能量分散谱术对样品进行了表征。讨论了不同种类的催化剂先体对产物形貌和生长机制的影响。     

堇青石负载稀土铈基催化剂催化燃烧苯的性能研究

以堇青石蜂窝陶瓷为载体,以过渡金属Mn(NO3)2和稀土金属Ce(NO3)2·6H2O盐为原料,采用柠檬酸浸渍法制备负载型MnCeOx混合氧化物催化剂,考察Mn与Ce的摩尔比、焙烧温度与时间以及柠檬酸用量对催化燃烧苯性能的影响,应用正交实验设计方案优化最佳制备工艺参数,并采用X射线衍射仪(XRD)、H2-TPR和扫描电镜(SEM)对催化剂进行表征与分析。实验结果表明n(Mn)∶n(Ce)=19∶21,焙烧时间为7h,n(Mn+)∶n(柠檬酸)=6∶1的催化剂表现出最佳的催化活性,在300℃及体积空速为20000h-1条件下,催化燃烧浓度为1.5×10-3的苯,催化转化率可达99.1%。     

溶液燃烧制备镧基钙钛矿及其催化碳烟燃烧性能

采用溶液燃烧法制备不同B位过渡金属元素(Mn、 Fe、 Co、 Ni)的La基钙钛矿(LaMO₃)催化剂,并考察少量Sr部分取代La对催化剂性能的影响;通过XRD、 SEM、 BET、 H₂-TPR、XPS方法对催化剂进行理化性质表征,采用程序升温氧化(TPO)技术评估催化剂催化碳烟燃烧的性能。结果表明：溶液燃烧法制备的La基催化剂具有典型的钙钛矿结构,少量Sr掺杂不改变催化剂的晶型;Sr掺杂LaMnO₃引起的电荷不平衡由增加的Mn⁴⁺补偿,Sr掺杂LaCoO₃使吸附氧量明显提高;La_0.9Sr_0.1MnO₃和La_0.9Sr_0.1NiO₃的氧化还原性能相比掺杂Sr之前的有所下降,La_0.9Sr_0.1FeO₃表面吸附氧物种量增多,催化剂的低温氧化还原性提升;气氛中NO_x     

锰基催化剂的制备及其对气相邻二氯苯的催化燃烧性能

二噁英类含氯挥发性有机物（Cl-VOC）是毒性很强的环境污染物,为了筛选用于催化燃烧Cl-VOC的高效、稳定的催化剂,采用共沉淀法制备了（Fe、Co、Cu、V）-Mn催化剂,并负载于堇青石载体上,用邻二氯苯作为模型化合物对其催化性能进行评价,结果发现Cu-Mn/堇青石催化剂对气相邻二氯苯的催化燃烧性能最好。XRD结果显示Cu-Mn/堇青石催化剂煅烧之后有新的尖晶石CuMn2O4晶相出现;SEM结果表明Cu-Mn/堇青石催化剂颗粒分散均匀;反应前后EDS对比结果表明,反应后催化剂表面残留有少量氯,但是,寿命测试表明持续反应20h,邻二氯苯的降解率能稳定在65%,说明Cu-Mn/堇青石催化剂用于催化燃烧含氯有机挥发物具有较好的应用前景。     

SnO（Sn）/泡沫镍整体催化剂的制备和催化活性

以泡沫镍为载体制备一系列活性组分为SnO和Sn的整体催化剂,测定了催化剂对邻苯二甲酸二(2-乙基己)酯(DOP)合成反应的催化活性,研究了电镀电流密度、电镀温度和焙烧处理对催化性能的影响,以及整体催化剂的寿命和失活的原因.结果表明,所制备的SnO(Sn)/泡沫镍整体催化剂对DOP的合成有很好的催化活性和选择性.用整体催化剂Sn/Ni-3(300)催化DOP的合成反应,在1h的反应时间内邻苯二甲酸酐的转化率达到96.75%;反应平衡时合成的产物中DOP的选择性达到97%以上.SnO(Sn)/泡沫镍整体催化剂使用后很容易从反应体系中分离,不需要任何处理即可重复使用多次.     

FeO_x对Mn-Ti复合氧化物催化剂催化燃烧氯苯性能的影响

采用溶胶-凝胶法制备了一系列不同Fe含量的MnOx-TiO2催化剂,使用氢气程序升温还原(H2-TPR)、X射线光电子能谱(XPS)、比表面积测定(BET)和X射线衍射(XRD)等技术对其进行了表征,考察了该类催化剂催化燃烧氯苯(CB)的活性和稳定性。催化活性测试结果表明,Fe的添加改善了MnOxTiO2催化剂的活性,同时显著提高了该催化剂的稳定性。表征结果表明,适量FeOx的添加能明显提高催化剂的比表面积,促进了各活性组分的分散,提高了催化剂表面活性氧物种和晶格氧的数量,使催化剂表面的氧化能力大幅度提高,从而提高了FeOx-MnOxTiO2催化剂的活性和稳定性。     

Synthesis of SnO(Sn)/Ni foam monolithic catalysts and their catalytic activity

以泡沫镍为载体制备一系列活性组分为SnO和Sn的整体催化剂,测定了催化剂对邻苯二甲酸二(2-乙基己)酯(DOP)合成反应的催化活性,研究了电镀电流密度、电镀温度和焙烧处理对催化性能的影响,以及整体催化剂的寿命和失活的原因. 结果表明,所制备的SnO(Sn)/泡沫镍整体催化剂对DOP的合成有很好的催化活性和选择性.用整体催化剂Sn/Ni-3(300)催化DOP的合成反应,在1h的反应时间内邻苯二甲酸酐的转化率达到96.75%;反应平衡时合成的产物中DOP的选择性达到97%以上.SnO(Sn)/泡沫镍整体催化剂使用后很容易从反应体系中分离,不需要任何处理即可重复使用多次.     

Influence of physicochemical treatments on spent palladium based catalyst for catalytic oxidation of VOCs

To recycle the spent catalyst for the removal of VOCs, the benzene, toluene, and xylene (BTX) complete oxidations were studied over pretreated palladium based spent catalyst in a fixed bed flow reactor system at atmospheric pressure. Two different pretreatment methods with gas (air and hydrogen) and acid aqueous solution (HCl, H(2)SO(4), HNO(3), H(3)PO(4) and CH(3)COOH) were used to investigate the catalytic activity of spent catalyst. The properties of the spent and pretreated Pd based catalyst were characterized by XRD, BET, TEM, ICP, and XPS. The results of light-off curves indicate that the catalytic activity of toluene oxidation for pretreated samples is in the order of hydrogen>air>HNO(3)>CH(3)COOH>H(2)SO(4)>H(3)PO(4)>HCl. In addition, the air and the acid aqueous pretreated catalyst activities were significantly decreased compared to that of the spent (or parent) catalyst. Moreover, hydrogen pretreated (or reduced) catalysts having mainly metallic form show the best performance in removing the toluene vapours compared to other pretreated samples. The reduction temperature made a significant difference in the catalytic performance of the spent catalyst pretreated with hydrogen. XPS results clearly supported that the palladium state of the spent catalysts pretreated at 300 degrees C was shifted more toward metallic form than other reduced catalysts. Furthermore, the results of a long-term test and catalytic activity of aromatic hydrocarbons also supported that the hydrogen pretreated spent catalyst was a good candidate for removing toxic compounds.     

Sulphur poisoning of palladium catalysts used for methane combustion: effect of the support

Four different supported palladium catalysts (using alumina, silica, zirconia and titania as supports), prepared by incipient wetness impregnation, were tested as catalysts for methane oxidation in presence of sulphur dioxide. The catalyst supported on zirconia showed the best performance, whereas the silica-supported one showed the fastest deactivation. Temperature-programmed desorption experiments of the poisoned catalysts suggest that SO(2) adsorption capacity of the support plays a key role in the catalyst poisoning. In order to study the effect of promoters, expected to improve the thermal stability and thioresistance of the catalyst, commercial zirconia modified by yttrium and lantane was tested as supports. It was found that the presence of these promoters does not improve the performance of the zirconia-supported catalyst. A deactivation model -- considering two different active sites (fresh and poisoning), pseudo-first order dependence on methane concentration and poisoning rate depending on sulphur concentration and fraction of non-poisoned palladium -- was used for modelling the deactivation behaviour.     

Carbonized tantalum catalysts for catalytic chemical vapor deposition of silicon films

Catalytic chemical vapor deposition (Cat-CVD) has been demonstrated as a promising way to prepare device-quality silicon films. However, catalyst ageing due to Si contamination is an urgency to be solved for the practical application of the technique. In this study, the effect of carbonization of tantalum catalyst on its structure and performance was investigated. The carbonized Ta catalyst has a TaC surface layer which is preserved over the temperature range between 1450 and 1750 °C and no Si contamination occurs on the catalyst after long-term use. Si film prepared using the carbonized Ta catalyst has a similar crystal structure to that prepared by uncarbonized Ta catalyst. Formation of the TaC surface layer can alleviate the ageing problem of the catalyst, which shows great potential as a stable catalyst for Cat-CVD of Si films.