MoO_3/Al_2O_3、MoO_3/TiO_2与NiO-MoO_3/TiO_2催化剂上活性相还原行为的XPS考察

STUDY ON REDUCTION BEHAVIOURS OF MOLYBDENA ON MoO_3/Al_2O_3, MoO_3/TiO_2 AND NiO-MoO_3/TiO_2 SYSTEMS BY XPS

石化工业中广泛使用的加氢脱硫(简称HDS)催化剂大多数是以γ-Al_2O_3为担体,以MoO_3或WO_3为主要活性组份,添加CoO或NiO为助剂的多组份催化剂。过去对HDS催化剂本质做了大量的研究,在研究中应用了XPS等许多现代物理方法近。

The H_2 reduction behaviours of MoO_3/Al_2O_3, MoO_3/TiO_2 and NiO-MoO_3/TiO_2 samples prepared by impregnation method were studied at various temperatures for different times by XPS technique. The recored XPS spectra of Mo3d from those samples were treated by computer curve fittingprogram to measure the distribution of various molybdenum oxide species with different valence states. The results of computer fitting shows that there areMo(Ⅵ), Mo(Ⅴ)and Mo(Ⅳ) on the all of reduced samples. However, after H_2 reductonin same way, the percentage of low valence species Mo(Ⅴ) and Mo(Ⅳ) on the MoO_3/TiO_2 is much higher than on the MoO_3/Al_2O_3 (Fig.2). For example, after H_2 treatment at 500℃ for 2 hrs., Mo(Ⅳ) species on the surface of MoO_3/TiO_2 sample is about 60% and it is three times higher than what is found on the MoO_3/Al_2O_3 sample. In addition, the reduction of molybdena on TiO_2 support is much easier and faster than on Al_2O_3 support (Fig.3). Addition of NiO further promotes the reduction of molybdena to cause the starting reduction temperature producing Mo(Ⅳ) and Mo(Ⅴ) to be decreased about 100℃. and 80% of molyb dena on NiO-MoO_3/TiO_2 support could be reduced to Mo(Ⅳ) (Fig.2). A detail discussion about the interaction between molybdena and carries was presented. It was suggested that TiO_2 is certainly involved in the reduction and oxidation process of molybdenum oxide species on the surface of it.