Hβ负载Mo基磷化物和硫化物加氢开环催化性能  

Hydrogenation and Ring Opening Catalytic Performances of H β SupportedMo-Based Phosphide and Sulfide

作　　者：李微 李翔 彭冲 盛强 尚森森 LI Wei;LI Xiang;PENG Chong;SHENG Qiang;SHANG Sensen(Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization,College of Chemical Engineering and Materials Science,Tianjin University of Science and Technology,Tianjin 300457,China;State Key Laboratory of Fine Chemical Engineering,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]天津科技大学化工与材料学院天津市卤水化工与资源生态化利用重点实验室,天津300457 [2]大连理工大学化工学院精细化工国家重点实验室,辽宁大连116024

出　　处：《石油学报（石油加工）》2024年第5期1194-1202,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21673029,22108207和22122807);重质油国家重点实验室开放基金项目(SKLHOP202202005);天津市自然科学基金重点项目(19JCZDJC31700)资助。

摘　　要：以Hβ分子筛为载体制备了负载型MoP以及Mo和NiMo硫化物催化剂(分别记作MoP/Hβ、MoS_(2)/Hβ和NiMoS_(2)/Hβ),采用X射线衍射(XRD)、吡啶吸附红外光谱(Py-IR)等手段对催化剂进行表征。以十氢萘作为模型化合物,在温度310℃、氢气压力4.0 MPa、质量空速(MHSV)3.2 h^(-1)和氢/油体积比1000的条件下考察催化剂的加氢开环反应性能。分析表征结果表明:与Hβ分子筛酸性相比,MoP/Hβ、MoS_(2)/Hβ和NiMoS_(2)/Hβ催化剂的酸性均有降低。加氢开环反应性能评价结果表明:MoP/Hβ活性和稳定性均优于MoS_(2)/Hβ和NiMoS_(2)/Hβ;硫化物催化剂在反应初期失活明显,主要归因其氢解活性的降低,金属中心和酸中心可能协同参与了催化十氢萘的缩环和开环反应。十氢萘主要通过缩环反应路径开环,由金属中心催化的直接氢解反应是次要路径,十氢萘的氢解反应优先通过金属环丁烷机理进行。与MoS_(2)/Hβ相比,十氢萘在MoP/Hβ与NiMoS_(2)/Hβ上的氢解反应通过金属环丁烷机理发生的比例更高。The supported MoP as well as Mo and NiMo sulfide catalysts were prepared using Hβzeolite as the support(denoted as MoP/Hβ,MoS_(2)/Hβ,and NiMoS_(2)/Hβ,respectively),which were characterized by techniques such as X-ray diffraction(XRD)and pyridine-adsorbed infrared spectrometry(Py-IR).The hydrogenation and ring opening performances of the catalysts were evaluated using decalin as the model compound at the temperature of 310℃,H 2 pressure of 4.0 MPa,mass hourly space velocity(MHSV)of 3.2 h^(-1)and hydrogen/oil volume ratio of 1000.The analysis and characterization results show that the acidities of MoP/Hβ,MoS_(2)/Hβ,and NiMoS_(2)/Hβare lower than that of Hβ.The performance evaluation results of ring opening reactions demonstrate that both the activity and stability of MoP/Hβare superior to those of MoS_(2)/Hβand NiMoS_(2)/Hβ.The quick deactivation of sulfide catalysts at the beginning of the ring opening of decalin is due to a decrease in their hydrogenolysis activity.The metal and acid sites are likely all involved in the ring contraction and ring opening of decalin.The ring opening of decalin occurs mainly through the ring contraction pathway,and the direct hydrogenolysis of decalin catalyzed by metals is a minor pathway.The metallocyclobutane mechanism is preferred for the hydrogenolysis of decalin over all the catalysts studied.Compared with the situation over MoS_(2)/Hβ,the hydrogenolysis of decalin is more likely to occur over MoP/Hβand NiMoS_(2)/Hβby means of metallocyclobutane mechanism.

关 键 词：HΒ分子筛 MOP MoS_(2) NiMo硫化物 十氢萘 开环反应 双功能催化剂 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]