Mixed oxide supported hydrodesulfurization catalysts—a review

Support effects form important aspect of hydrodesulfurization (HDS) studies and mixed oxide supports received maximum attention in the last two decades. This review will focus attention on studies on mixed oxide supported Mo and W catalysts. For convenience of discussion, these are divided into Al₂O₃ containing mixed oxide supports, TiO₂ containing mixed oxide supports, ZrO₂ containing mixed oxide supports and other mixed oxide supports containing all the rest. TiO₂ containing mixed oxides received maximum attention, especially TiO₂–Al₂O₃ supported catalysts. A brief discussion about their prospects for application to ultradeep desulfurization is also included. An overview of the available literature with emphasis on research carried out in our laboratory form the contents of this publication.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

高质量ZnO薄膜的退火性质研究

在LP－MOCVD中，我们利用Zn(C2H5)2作Zn源，CO2作氧源，在（0002）蓝宝石衬底上成功制备出皮c轴取向高度一致的ZnO薄膜，并对其进行500℃-800℃四个不同温度的退火。利用XRD、吸收谱、光致发光谱和AFM等手段研究了退火对ZnO晶体质量和光学性质的影响。退火后，（0002）ZnO的XRD衍射峰强度显著增强，c轴晶格常数变小，同时（0002）ZnOX射红衍射峰半高宽不断减小表明晶粒逐渐增大，这与AFM观察结果较一致。由透射谱拟合得到的光学带隙退火后变小，PL谱的带边发射则加强，并出现红移，蓝带发光被有效抑制，表明ZnO薄膜的质量得到提高。     

The Synthesis of Sulfated Titanium Oxide Nanotubes

TiO₂ nanotubes can be prepared in gram quantities by treating anatase TiO₂ powder with concentrated NaOH solution. These TiO₂ nanotubes acquired strong acidity after being impregnated with sulfuric acid solution and calcined at 300 °C. The anatase TiO₂ powder used to prepare the nanotube did not catalyze the esterification between cyclohexanol and acetic acid, while sulfated TiO₂ nanotubes were very reactive toward the esterification reaction.     

Growth Stresses in the Oxide Scales on TiAl Alloys at 800 and 900°C

In the oxidation of TiAl alloys, the role of scale-growth stresses formed during oxidation has, thus far, been unknown. In the present paper the oxide-growth stresses were investigated by the deflection-test method in monofacial oxidation (DTMO) accompanied by acoustic-emission measurements. On unmodified surfaces the growth stresses are compressive and reach levels of around –100 MPa. At the same time, significant acoustic emission occurs indicating that even under isothermal conditions, stresses are relieved by a scale-cracking mechanism. For oxide scales on TiAl surfaces, which had been ion implanted with chlorine before oxidation, a very thin protective alumina layer is formed which, however, develops growth stresses in the range of several GPa, accompanied by intensive acoustic emission. In all stress–time curves, a dynamic situation is observed. This consists of phases of stress relief by scale microcracking and phases of stresses increase due to crack healing and further oxide growth. As a result, the level of stress as a function of oxidation time, is characterized by an oscillating course.     

熔融碳酸盐燃料电池阴极材料的导电性

通过交流阻抗方法研究了熔融碳酸盐燃料电池阴极材料锂镍氧化物、锂钴氧化物和锂铁氧化物的导电性能。结果表明:锂镍氧化物电极的导电性最好,锂钴氧化物电极的导电性次之,锂铁氧化物电极的导电性最差;它们的导电性都随着温度的升高而按指数规律增加;在合成锂钴氧化物(或锂铁氧化物)的过程中,使Li2CO3轻微过量,可以提高锂钴氧化物(或锂铁氧化物)电极的导电性,而且在同一温度下,随着nLi∶nCo(或nLi∶nFe,摩尔比)值的增大,锂钴氧化物(或锂铁氧化物)电极的导电性显著增加。     

Relating catalyst structure and composition to the water–gas shift activity of Cu–Zn-based mixed-oxide catalysts

In order to investigate the effect of cerium oxide on Cu–Zn-based mixed-oxide catalysts four catalyst samples were characterized by means of XRD, in situ XANES and thermogravimetric analysis. The activity of the catalyst samples was tested for the forward water–gas shift reaction. Cerium oxide was found to increase the crystallinity of the ZnO phase indicating a segregation of the Cu and ZnO phases. The TOF of the water–gas shift reaction based on chemisorption data was found to be independent of composition and preparation conditions of the four catalyst samples. In contrast, the catalyst stability depends on composition and preparation conditions. Cerium oxide impregnated before calcination of the hydrotalcite-based Cu–Zn precursors leads to a more stable water–gas shift catalyst.     

Formation and electronic structure of interface

In the present work the formation of the interface between polycrystalline silver and thin films of titanium oxide was studied with photoelectron spectroscopy (XPS, UPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Titanium oxide was deposited stepwise on 100 nm thick silver films by reactive magnetron sputtering allowing to study the evolution of the interface formation process. The process involves two steps: formation of thin layer of silver oxide and subsequent growth of the TiO₂ film. For better understanding of the silver oxidation process, pure silver films were exposed to a low temperature Ar/O plasma for different time intervals providing a possibility to investigate early stages of the oxide film growth.     

降低气体悬浮焙烧炉焙烧过程中Al_2O_3粒度破损的措施

为了降低气体悬浮焙烧炉焙烧过程中Al_2O_3粒度的破损,对气体悬浮焙烧炉焙烧过程中氧化铝粒度的影响因素进行了分析,提出了降低粒度破损的一些措施。