制备方法对WO_3/ZrO_2结构的影响

用XRD、比表面测定、LRS定性和定量的方法对用Zr（OH）4和已晶化的ZrO2作载体制得的两类WO3／ZrO2催化剂进行了表征．揭示了样品比表面、载体物相、活性组分的存在状态与制备方法、WO3含量、焙烧温度之间的关系．结果表明，WO3能单层分散在ZrO2上；单层覆盖在Zr（OH）4上的WO3使载体在焙烧时晶粒生长受阻，形成介稳的四方ZrO2，并阻止载体微粒间的烧结，使从Zr（OH）4出发制得的WO3／ZrO2比表面明显增大，在WO3含量达到单层分散容量时以上作用表现得最充分；WO3与Zr（OH）4（或四方ZrO2）在高温（～800℃）可能发生了某种化学结合，开创出超强酸位．用以上观点可对文献中已报导的主要实验事实作出较满意的解释.     

MoO3和CuCl在γ-Al2O3表面分散速度和分散机理的研究

It has been shown that many oxides and salts can disperse spontaneously onto supports with large surface area~[1]. A typical example studied widely is the dispersion of MoO_3 on γ-Al_2O_3. However, the research work about the dispersion mechanism and kinetics is quite few.Knozinger etc.~[2] suggested that the dispersion of MoO_3 onto the surface of γ-Al_2O_3 may occur through a "gas phase transport" mechanism mainly by assuming an intermediate MoO_2(OH)_2(g), and the presence of water is necessary. Their conclusion was based on a fact that after heating a mixture of MoO_3 and γ-Al_2O_3 in the presence of H_2O vapour at 450 ℃, the characteristic peak at 950 cm~(-1) of monolayer dispersed MoO_3 in Laser Raman Spectrum (in situ) appears, but after heating the mixture in dry oxygen, it can not be observed...     

制备高比表面负载型催化剂的一种新方法

In this paper, a new way to increase the specific surface areas of supported catalysts has been suggested. The results for MoO_3/ZrO_2, WO_3/ZrO_2, CuO/ZrO_2, SO_4~(2-)/ZrO_2, NiO/ZrO_2, Fe_2O_3/ZrO_2, Fe_2(SO_4)_3/ZrO_2, MoO_3/TiO_2, WO_3/TiO_2, SO_4~(2-)/TiO_2, NiSO_4/TiO_2, NiO/TiO_2, V_2O_5/TiO_2 etc. systems show that the specific surface areas of the samples, prepared by impregnating some hydroxides then calcinating at high temperature, are much larger than those of the samples prepared with a traditional method——impregnating their oxides calcinated at the same temperature. Using this way, the specific surface areas of some supported catalysts can increase by several times. The surface areas of some supports such as zirconia and titania are not large enough, and they are easy to sinter at high temperature. In these cases, the advantage of of this preparation method is fully displayed, and the specific surface areas of the resulting zirconia-or titania-supported catalysts can compare favourably with those of the catalysts prepared from some classical supports (such ar γ-Al_2O_3, SiO_2).In addition, it has been proved by means of XPS, XRD, LRS, and DTA that as an active component disperse on a support as a monolayer and its content comes up to its monolayer dispersion capacity, the specific surface area of the obtained catalyst would be the largest. We suggest a mechanism that an active component covered on a support can not only segregate its particles, but also hinder the surface diffusion of support, and as a result, its crystalline growth, an accompanying phase transformation and inter-crystalline sintering are all retarded.     

制备方法对WO3/ZrO2结构的影响

WO3/ZrO2 catalysts prepared from Zr(OH)4 and crystallized ZrO2 have been characterized by means of XRD, LRS (qualitative and quantitative), and the specific sufrace area has been measured. The influence of the preparation method, the contents of WO3 in the samples and the calcination tempearture on the specific surface areas of the samples, the phase of support and the structural states of active component has been studied. The results show: (1) WO3 can disperse on ZrO2 as a monolayer; (2) WO3 dispersed on Zr(OH)4 as a monolayer retards the crystalline growth of the support on calcination, makes it crystallizing into a metastable tetragonal modification, and prevents the inter- crystalline sintering between the crystallites of ZrO2. These factors would result in an increase in the specific surface area of WO3／ZrO2 prepared from Zr(OH)4. As the content of WO3 in the sample comes up to its monolayer capacity, this effect is displayed most fully. A chemical reaction can occur between WO3 and Zr(OH)4 (or the tetragonal ZrO2) at a high temperature(800℃),producing some superacid sites on the surface. By these views, the main experimental facts published in the literatures can been interpreted satisfactotily.     

MoO_3和CuCl在γ-Al_2O_3表面分散速度和分散机理的研究

许多氧化物和盐能在大比表面载体上自发分.MoO_3在γ-Al_2O_3表面的分散是研究得最多的典型例子.然而,对于分散机理和分散动力学的研究还很少。Knozinger等曾提出,MoO_3在γ-Al_2O_3表面的分散是通过中间物MoO_2(OH)_2的气相     

TiO_2在γ-Al_2O_3的单层分散态

近年来文献报道,用TiO_2(锐钛矿)改性的γ-Al_2O_3,作为钼系加氢脱硫或脱氮催化剂的载体,可明显改善催化剂的性能。因此,TiO_2在γ-Al_2O_3表面上的存在状态和性质已成为重要的研究课题。我们曾对用气相吸附法制备的TiO_2/γ-Al_2O_3复合载体中的TiO_2在γ-Al_2O_3表面上的存在状态作了初步研究,发现TiO_2在γ-Al_2O_3(Sg=211.6m~2、g)表面上有一分散阈值     

制备高比表面负载型催化剂的一种新方法

制备具有大比表面、适宜孔结构的催化剂一直是催化剂研究的重要课题之一.近年,氧化锆、氧化钛载体以其独特性能引起多方面的关注.然而,这两种载体不但本身比表面较小,而且在高温灼烧时比表面急剧下降,所以很难制成高比表面催化剂,极大地限制了它们的应用.本文提出一种制备高比表面负载型催化剂的新方法,它特别适用于TiO_2、ZrO_2.它是在以下两个想法的基础上提出的.(1)我们在工作中曾发现,将仲钼酸铵加到Ti(OH)_4中,经500℃、4小时焙烧,所得的MoO_3/TiO_2(MoO_3质量分数为13.0%)比表面可达133m~2·g~(-1).而用仲钼酸铵浸渍已晶化     

复合载体TiO2/SiO2的气相吸附法制备及MoO3在其表面上的分散状态

用气相流动吸附法制备了TiO_2/SiO_2复合载体,用浸渍法制备了MoO_3/(TiO_2/SiO_2)催化剂。应用XRD和LRS等技术研究了TiO_2在SiO_2表面及MoO_3在TiO_2/SiO_2表面上的分散状态。结果表明,TiO_2在复合载体中的含量低于其分散阈值时,它在SiO_2表面呈单层但非密置单层分散;MoO_3在催化剂中的含量低于其分散阈值时,它在复合载体表面亦呈单层但非密置单层分散。TiO_2与SiO_2之间、MoO_3与TiO_2/SiO_2之间相互作用都较弱。TiO_2在SiO_2表面的分散可改善MoO_3的分散状态,提高MoO_3在SiO_2表面上的分散阈值。     

气相吸附法制备复合载体TiO_2/γ-Al_2O_3及TiO_2在γ-Al_2O_3表面的分散状态

采用气相流动吸附法,以N_2为载气携带TiCl_4通过γ-Al_2O_3床,使TiCl_4吸附在γ-Al_2O_3表面上,经水解、干燥和焙烧制得TiO_2/γ-Al_2O_3复合载体。用XRD,LRS和TEM等表征手段研究了TiO_2在γ-Al_2O_3表面上的分散状态。结果表明,TiO_2在γ-A1_2O_3表面有一分散阈值(0.168 g TiO_2/g γ-Al_2O_3,在阈值以下TiO_2以单层或亚单层分散形式存在,在阈值以上则出现晶相,未发现有体相化合物生成。测定了TiCl_4穿透曲线和吹扫曲线,为用气相流动吸附法制备TiO_2/γ-Al_2O_3复合载体工艺条件的选择提供了基础。