磷化钨催化剂的表征和加氢精制性能  

CHARACTERIZATION AND HYDROTREATING PERFORMANCE OF TUNSTEN PHOSPHIDE CATALYST

作　　者：孙桂大[1] 李翠清[1] 李凤艳[1] 周志军[1] 

机构地区：[1]北京石油化工学院,北京102617

出　　处：《石油学报（石油加工）》2005年第3期54-60,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展规划(G2000048);中国石油化工集团公司(X501022)资助项目

摘　　要：采用在H2气中程序升温还原磷化反应的方法合成了磷化钨(WP)和负载型磷化钨催化剂(WP/γAl2O3),用XRD、TEM和XPS等技术表征了合成的催化剂,并考察了WP催化剂的加氢精制性能。采用TGDTA手段研究了WP催化剂的还原磷化过程,证明其为一步反应过程。WP催化剂钝化时,其表面层能被氧化,但不改变其体相结构。活性组分W和γAl2O3载体之间有较强的相互作用,使γAl2O3表面上的W组分在催化剂合成的温度下不能完全还原为磷化物而形成Al-O-W-P结构。WP/γAl2O3催化剂具有优良的加氢脱氮(HDN)和加氢脱硫(HDS)性能,特别是对大分子含氮有机化合物有更高的脱氮活性。助剂Co和Ni对WP/γAl2O3催化剂具有助催化作用,但助剂Ni对吡啶的脱氮性能有抑制作用。含有助剂Ni的WP/γAl2O3催化剂对柴油显示了比硫化态的工业催化剂更良好的HDS性能。Tungsten phosphide (WP) and γ-Al2O3-supported tungsten phosphide catalysts (WP/γ-Al2O3) were synthesized by phosphiding with H2 in process of temperature programmed reduction and characterized by XRD, XPS and TEM. The reduction-phosphiding of the precursors of WP catalysts was investigated and proved one-step reaction process by TG-DTA technique. The passivating process caused surface oxidation of WP catalysts, but did not change their crystal structure. Due to a stronger interaction between W species and γ-Al2O3 the W species on the surface of γ-Al2O3 could be not completely phosphided and were converted to the active species with the Al-O-W-P structure at the synthesis temperature of the catalysts. The WP/γ-Al2O3 catalysts possessed high and stable activities of HDS and HDN, especially a better activity of HDN for large organic compounds containing nitrogen. Co and Ni could promote the hydrotreating activities of the WP/γ-Al2O3 catalysts, but Ni inhibited the pyridine HDN activity. The Ni-WP/γ-Al2O3 catalyst had higher HDS activity of diesel oil than the industrial sulphide catalyst.

关 键 词：磷化钨 加氢脱硫 加氢脱氮 镍 钴 

分 类 号：O643.32[理学—物理化学]