摘要
以具有不同孔结构的十二元环微孔分子筛为酸性组分,制备了含分子筛的CoMoP/Al_2O_3加氢催化剂,采用固定床高压微反装置考察了4,6-二甲基二苯并噻吩的加氢脱硫反应,并通过N_2吸附-脱附、吡啶吸附红外、X射线衍射(XRD)和扫描电镜(SEM)等表征手段对几种分子筛样品进行物化性质分析。结果表明,分子筛的孔结构和酸中心的可接近性是影响含分子筛催化剂上总反应活性及各路径产物分布的主要因素。在反应温度300℃、H)2分压4.0MPa、H)2/原料油体积比为500的条件下,含Y分子筛催化剂的总反应活性及脱硫率最高。与β分子筛相比,晶粒尺寸更小的Nβ分子筛上酸中心的可接近性提高,含Nβ分子筛催化剂的总反应活性与酸催化反应活性明显提高。
A series of catalysts were prepared by using the 12-membered ring zeolites with different pore structures as acidic components.The catalytic performance of CoMoP catalysts containing zeolites(CoMoP/Al 2O 3-zeolite)was evaluated by the hydrodesulfurization of 4,6-dimethyldibenzothiophene(4,6-DMDBT).Zeolite samples were characterized by N 2 adsorption-desorption,pyridine-FTIR,X-ray diffraction(XRD)and scanning electron microscopy(SEM)techniques.Results show that the pore structure and accessibility of acid sites of zeolites are the main factors that influence both the catalytic activity and product selectivity through different reaction pathways over CoMoP/Al 2O 3-zeolite catalysts.Among CoMoP/Al 2O 3 and all CoMoP/Al 2O 3-zeolite catalysts,CoMoP/Al 2O 3-Y exhibits the highest conversion and sulfur removal rate of 4,6-DMDBT,under the condition of temperature of 300℃,H 2 partial pressure of 4.0 MPa and H 2/oil volume ratio of 500.The catalyst containing Nβzeolite with smaller crystal size shows higher conversion of 4,6-DMDBT and acid-catalyzed reaction activity than that ofβcatalyst,due to the higher accessibility of acid sites.
作者
刘诗哲
李明丰
王永睿
张乐
杨平
李大东
LIU Shizhe;LI Mingfeng;WANG Yongrui;ZHANG Le;YANG Ping;LI Dadong(Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China)
出处
《石油学报（石油加工）》
EI
CAS
CSCD
北大核心
2018年第5期849-855,共7页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
国家重点研发计划项目(2017YFB0306600)资助
