不同载体负载的磷化钨催化剂加氢脱硫和降烯烃性能研究  

Hydrodesulfurization and reducing-olefin of tungsten phosphide catalysts over different supports

作　　者：李翠清[1] 魏军[1] 孙桂大[1] 周志军[1] 王红伟[1] 李凤艳[1] 

机构地区：[1]北京石油化工学院绿色化学与催化材料研究所,北京102617

出　　处：《燃料化学学报》2007年第6期767-771,共5页Journal of Fuel Chemistry and Technology

基　　金：国家重点基础研究发展规划(973计划;G2000048003);北京市自然科学基金(2052009);北京市教委资助(KM200510017003);中国石油化工股份有限公司资助(X04009)。

摘　　要：A series of supported tungsten phosphide catalysts of 30% W (counted in WO3) supported over γ-Al2O3, TiO2, SiO2, γ-Al2O3/SiO2, γ-Al2O3/TiO2 and SiO2/TiO2, respectively, were prepared by temperature-programmed reduction of the corresponding phosphates. The samples were characterized by XRD, BET and TG analysis. The activity of these catalysts were determined in the hydrodesulfurization (HDS) of thiophene and simultaneous thiophene HDS and cyclohexene reducing-olefin (HDY), respectively. The results showed that WP species could not be clearly detected in tungsten phosphide over the supports containing alumina, while species with a structure of -Al-O-W-P was obviously formed. TiO2 could play a better role in restraining the generation of WP species on the surface of composite supports than that of SiO2. TG results indicated that the starting reaction temperature of phosphiding-reduction of the supported tungsten phosphide precursor was probably determined by the structure of catalyst, while the extent of phosphiding-reduction was probably related to the interaction between support and active species and between two supports. W species on the surface of catalysts over the support containing alumina could not be completely reduced to WP and some W species may be existed in the form of -Al-O-W-P. Tungsten phosphide over different supports showed better cyclohexene HDY conversion than that of thiophene HDS conversion. The -Al-O-W-P species favor the thiophene HDS reaction and also favor the simultaneous thiophene HDS and cyclohexene HDY reactions. Besides of the TiO2, thiophene HDS activities of supported tungsten phosphide catalysts decreased to some extent by adding cyclohexene.A series of supported tungsten phosphide catalysts of 30% W (counted in WO3) supported over γ-Al2O3, TiO2, SiO2, γ-Al2O3/SiO2, γ-Al2O3/TiO2 and SiO2/TiO2, respectively, were prepared by temperature-programmed reduction of the corresponding phosphates. The samples were characterized by XRD, BET and TG analysis. The activity of these catalysts were determined in the hydrodesulfurization (HDS) of thiophene and simultaneous thiophene HDS and cyclohexene reducing-olefin (HDY), respectively. The results showed that WP species could not be clearly detected in tungsten phosphide over the supports containing alumina, while species with a structure of -Al-O-W-P was obviously formed. TiO2 could play a better role in restraining the generation of WP species on the surface of composite supports than that of SiO2. TG results indicated that the starting reaction temperature of phosphiding-reduction of the supported tungsten phosphide precursor was probably determined by the structure of catalyst, while the extent of phosphiding-reduction was probably related to the interaction between support and active species and between two supports. W species on the surface of catalysts over the support containing alumina could not be completely reduced to WP and some W species may be existed in the form of -Al-O-W-P. Tungsten phosphide over different supports showed better cyclohexene HDY conversion than that of thiophene HDS conversion. The -Al-O-W-P species favor the thiophene HDS reaction and also favor the simultaneous thiophene HDS and cyclohexene HDY reactions. Besides of the TiO2, thiophene HDS activities of supported tungsten phosphide catalysts decreased to some extent by adding cyclohexene.

关 键 词：载体 磷化钨 噻吩 环己烯 加氢脱硫 加氢降烯 

分 类 号：O643[理学—物理化学]