摘要: In this work, the impact of CeOx doping on a TiO2-SiO2 supporter on the Ag based adsorptive desulfurization for Chinese standard diesel was studied. The dispersion and valence states of Ce, Ti and Ag species were characterized, and the impact of Ce doping was investigated. The results indicated that Ce species and Ti species were dispersed evenly on the surface of SiO2 via a novel co-impregnation method. Following CeOx doping, the Ag species were in the form of oxides (about 5nm) instead of metallic Ag particles (about 35nm), which is due to the large amount of coordinative unsaturated sites provided by the interaction between CeOx and TiO2, as well as the oxidation-reduction property of CeOx. The Ag in the active oxide state (Ag2O2) and dispersed evenly on the supporter could interact with sulfur compounds more favorably, and therefore showed a good performance in the adsorptive desulfurization. In both static batch and dynamic breakthrough desulfurization tests, Ag-CeOx/TiO2-SiO2 was proved to be a more efficient adsorbent compared with Ag-TiO2-SiO2. It was found that the desulfurization performance of Ag-TiO2-SiO2 exhibited an excellent improvement (22.5%) after being doped with CeOx. In the static equilibrium tests, the equilibrium sulfur capacity of Ag-CeOx/TiO2-SiO2 was up to 5.38mg/g for CN-II diesel (sulfur content 952.9mg/kg) and the sulfur content of the CN-IV diesel (sulfur content 39.0mg/kg) after desulfurization was less than 10mg/kg, which could meet the CN-V standard.
摘要: 在反应温度550℃、空速5000h-1和1.2% H2S浓度下,考察了反应气中添加CO2对负载型Mo基催化剂甲烷化活性的影响。结果表明,添加CO2会促进逆水煤气变换反应,从而降低MoO3/Al2O3催化剂的耐硫甲烷化活性。与MoO3/Al2O3催化剂相比,添加CO2对铈铝复合载体负载的Co-Mo双组分催化剂的影响较小。通过表征发现,添加CO2引起催化剂活性下降的主要原因是由于其增强了逆水煤气变换反应过程,使甲烷化过程可用氢气量减小。另外,逆水煤气变换反应生成的水会影响催化剂表面结构和组成。在连续加入10% CO2 20h后停止加入CO2,催化剂的耐硫甲烷化活性可以得到恢复,因此,认为CO2加入量低于10%时,对催化剂及甲烷化反应的影响是可逆的;但CO2加入量大于10%后由于生成的水量增大会破坏催化剂的结构并减少活性位,从而造成催化剂的不可逆失活。
摘要: 以碳微球作为硬模板、纳米Silicalite-1分子筛作为壳层,采用水热法合成了Silicalite-1空心球材料。采用XRD、SEM、FT-IR、N2吸附、29Si MAS NMR、TG、XPS等技术对催化剂的物相、形貌和性能等进行表征,发现该空心材料具有较高的结晶度、发达的多级孔道结构和丰富的表面羟基。与传统方法制备的Silicalite-1分子筛催化剂相比,Silicalite-1空心材料在环己酮肟Beckmann重排反应中表现出优异的催化性能,使环己酮肟的转化率达99%、己内酰胺的选择性达94%,同时催化剂保持极佳的稳定性。研究表明,Silicalite-1空心材料中具有的大量巢式硅羟基和末端硅羟基是Beckmann重排反应的主要活性位,且可通过简单焙烧再生实现羟基活性位的完全恢复。