载体孔径分布集中度对Ni-Mo催化剂上芘加氢反应的影响  

EFFECT OF CONCENTRATION OF CARRIER PORE SIZE DISTRIBUTION ON PYRENE HYDROGENATION REACTION OVER Ni-Mo CATALYST

作　　者：温昌盛 聂红 曾双亲 郭锦春 贾燕子 杨清河 Wen Changsheng;Nie Hong;Zeng Shuangqin;Guo Jinchun;Jia Yanzi;Yang Qinghe(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油炼制与化工》2024年第10期84-93,共10页Petroleum Processing and Petrochemicals

基　　金：国家重点研发计划项目(2021YFA1501204);中国石油化工股份有限公司合同项目(121020)。

摘　　要：采用NaAlO_(2)-Al(SO_(4))_(3)法制备得到拟薄水铝石,通过控制拟薄水铝石的老化时间来调节拟薄水铝石的晶粒尺寸,得到比表面积、孔体积、孔径基本相同,孔集中度有所差异的4种不同孔结构的载体。以芘作为模型化合物在高压微型固定床反应装置上考察了4种载体所制备Ni-Mo催化剂的芳烃加氢饱和性能。采用X射线衍射仪、X射线光电子能谱仪、透射电子显微镜和色谱-质谱联用仪等对拟薄水铝石、载体、催化剂进行表征。结果表明:随着老化时间的增加,拟薄水铝石的结晶度和晶粒尺寸增加;载体的比表面积、孔体积和最可几孔径相近,孔径分布集中度增加;表面总羟基数量和碱性羟基所占比例逐渐降低,氧化态催化剂金属和载体之间相互作用力降低,硫化后催化剂硫化度以及Ⅱ类多层活性相所占比例增加。芘的加氢评价结果表明,随着载体孔径分布集中度的增加,芘加氢转化率提高。说明硫化度和Ⅱ类活性相所占比例增加有利于提高催化剂加氢性能,载体孔径分布集中度提高后,8~10 nm孔所占的有效比表面积明显增加,更有利于分子扩散进入孔内接触到有效活性中心。Pseudo-boehmite was prepared by the NaAlO_(2)-Al(SO_(4))_(3) method,the grain size of the pseudo-boehmite was adjusted by controlling the aging time of the pseudo-boehmite,and four carriers with different pore structures were obtained with the same specific surface area,pore volume and pore size,but the pore size distribution was different.Pyrene was used as a model compound to investigate the hydrogenation saturation properties of the catalysts prepared by these four carriers on a high-pressure microreaction device.BET,XRD,XPS,TEM and GC-MS were used to characterize the pseudo-boehmite,support and catalyst.The results showed that with the increase of aging time,the crystallinity and grain size of the pseudo-boehmite increased,the specific surface,pore volume and maximum pore size of the support were similar,the pore size distribution concentration increased,the number of total hydroxyl groups on the surface and the proportion of basic hydroxyl groups decreased gradually,the interaction force between the oxidized metal and the support decreased,and the sulfidation degree of the catalyst and the proportion of class Ⅱ multilayer active phases increased after sulfidation.The hydrogenation evaluation results of pyrene displayed that the hydrogenation conversion rate of pyrene increased with the increase of the concentration of carrier pore size distribution.The results also indicated that the increase of sulfidation degree and the proportion of type Ⅱ active phase was conducive to improving the hydrogenation performance of the catalyst.With the increase of the concentration of pore size distribution,the effective specific surface of the 8-10 nm pores was obviously increased,which was more conducive to the molecules diffusion into the pores to contact active site.

关 键 词：拟薄水铝石 老化时间 加氢 孔径分布集中度 芘 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]