PHR系列固定床渣油加氢催化剂的研制开发与工业应用

中国石油石油化工研究院通过深入研究渣油原料的结构组成与加氢转化行为特征，成功开发出包括保护剂、脱金属剂、脱硫剂和脱残炭剂4大类共12个牌号的PHR系列固定床渣油加氢催化剂。在保护剂中构建了"毫米-微米-纳米"多级孔体系，其微米级孔（PHR-402、PHR-403催化剂）与纳米级孔（PHR-404催化剂）均为双峰分布，微米级孔（PHR-402、PHR-403催化剂）主要分布在1μm附近区域和30~200μm的较宽泛区域，纳米级孔（PHR-404催化剂）的集中孔径则分别约为13nm和250nm，纳米级孔中大于100nm的孔比例达到35%。脱金属剂具有双峰分布的孔结构及内高外低的活性金属含量分布，其"扩散孔"孔径达到微米级（2300nm），大于100nm的孔比例超过20%。工业应用结果表明，PHR系列渣油加氢催化剂具有高而稳定的脱硫、脱氮、脱残炭等活性，催化剂内部孔结构的利用率高，且床层压降更低，有利于延长装置运转周期。

Development and application of PHR fixed-bed residue hydrotreating catalysts

Through the study of the structural and composition of residual oil and its conversion behavior under hydrotreatment conditions, Petrochemical Research Institute (PRI) of PetroChina has developed 12 kinds of PHR fixed-bed residue hydrotreating catalysts, which can be classified as guard catalysts, hydrodemetallization (HDM) catalysts, hydrodesulfurization (HDS) catalysts and hydrodecarbonation(HDCCR) catalysts. The PHR guard catalysts feature multi-scale pore system as they contain milli-, micro-and nano-pores. The pores at both micrometre (existed in PHR-402 and PHR-403 catalysts) and nanometre(existed in PHR-404 catalyst) levels exhibit dual-peak distribution. The micro-pores(existed in PHR-402 and PHR-403 catalysts) are sized around 1μm and between 30-200μm, respectively. The nano-pores(existed in PHR-404 catalysts) are sized at about 13nm and 250nm, respectively. Those nano-pores with pore size above 100nm take over 35% of all the nano-pores. The PHR HDM catalysts have dual-peak distribution in pore size as well, and metals distribute in an inner high and outer low manner. The diffusion pores can achieve micrometre scale(up to 2300nm) with over 20% pores bigger than 100nm. The industrial application results of PHR catalysts suggest that they have excellent activity and stability on the HDS, hydrodenitrogenation(HDN) and HDCCR of residue oils. The efficient use of inner pores of catalysts is achieved. In addition, the process pressure drop of the PHR catalysts is extremely low, which is an advantage for the long term operation of hydrotreating units.