摘要
制备了一系列Co含量不同的CoMo/γ-Al_(2)O_(3)加氢处理催化剂,并通过X射线衍射、氢气程序升温还原、拉曼光谱、X射线光电子能谱和原位一氧化碳吸附傅里叶变换红外光谱等手段对催化剂进行了表征,考察Co含量对活性金属形貌性质和硫化态催化剂活性相结构的影响,并与催化剂的加氢脱硫活性和多环芳烃饱和活性相关联。结果表明:随着Co含量增加,催化剂表面形成更多的CoMoO_(4)物种;低结晶度的CoMoO_(4)物种在硫化过程中更易形成高活性CoMoS相,从而提高催化剂的加氢脱硫活性;但Co含量过高时,硫化后会生成较多脱硫活性低的Co_(9)S_(8)相并与CoMoS相产生竞争吸附,降低催化剂加氢脱硫活性;由于催化剂脱硫和加氢活性位并不相同,Co_(9)S_(8)相的形成并未降低催化剂的芳烃饱和活性。当催化剂CoO/MoO_(3)质量比为0.3时,催化剂的加氢脱硫活性最佳;当催化剂CoO/MoO_(3)质量比为0.4时,催化剂的多环芳烃饱和活性最好。
A series of CoMo/γ-Al_(2)O_(3)hydrotreating catalysts with different Co content were prepared and characterized by XRD,H_(2)-TPR,Raman,XPS and in-situ CO-FTIR analysis.The effect of Co content on the morphology of the active metal and the structure of active phase of the sulfided catalysts were investigated and correlated with the hydrodesulfurization(HDS)activity and polycyclic aromatic hydrocarbons(PAH)saturation activity of the catalysts.The results showed that with the increase of Co content,more CoMoO_(4)species were formed on the surface of the catalysts,and the CoMoO_(4)species with low crystallinity were more likely to form highly active CoMoS phase during sulfurization,thus improving the HDS activity of the catalyst.However,if the content of Co was too high,more Co_(9)S_(8)phase with low desulfurization activity would be formed and competitive adsorption with CoMoS phase would occur,which would decrease the HDS activity of the catalyst.Because the active sites of catalyst for desulfurization and hydrogenation were not the same,the formation of Co_(9)S_(8)phase did not reduce the aromatics saturation activity of the catalyst.When the mass ratio of CoO to MoO_(3)was 0.3,the catalyst had the best HDS activity,and when the mass ratio of CoO to MoO_(3)was 0.4,the catalyst has the best PAH saturation activity.
作者
孙进
郭蓉
陈晓贞
尹晓莹
段为宇
牛世坤
Sun Jin;Guo Rong;Chen Xiaozhen;Yin Xiaoying;Duan Weiyu;Niu Shikun(SINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co.,Ltd.,Dalian,Liaoning 116045)
出处
《石油炼制与化工》
CAS
CSCD
北大核心
2023年第6期32-38,共7页
Petroleum Processing and Petrochemicals
基金
辽宁省“兴辽人才计划”项目(XLYC2002102)
大连市高层次创新创业项目(2020RD10)。
关键词
氧化钴
氧化钼
加氢脱硫
多环芳烃饱和
活性相
cobalt oxide
molybdenum oxide
hydrodesulfurization
PHA saturation
active phase
