Co-Mo/SiO2-Al2O3润滑油加氢处理催化剂的制备

Preparation of Co-Mo/SiO2-Al2O3 catalyst for hydrotreating lubricating oil

  • 摘要: 以Pluronic P123作结构导向剂,采用Al(NO33-NaAlO2双水解法合成氧化铝,在成胶过程中加入正硅酸乙酯,制备硅质量分数分别为5%、10%、15%的SiO2-Al2O3载体,并通过共浸渍法制备出Co-Mo/SiO2-Al2O3润滑油加氢处理催化剂。通过XRD、N2吸附-脱附、Py-FTIR、NH3-TPD、H2-TPR、TEM和XRF等手段对载体及催化剂的性质进行表征。结果表明,硅质量分数为10%的SiO2-Al2O3具有优良的孔结构、较多的中强酸以及部分有序的介孔结构。以此为载体制备的Co-Mo/10% SiO2-Al2O3催化剂中,MoS2颗粒均匀地分散在载体上,具有更多的B酸性位和Ⅱ型CoMoS活性相。以减二线蜡油为原料油的固定床活性评价结果表明,生成油中主要组分为链烷烃与环烷烃;尤其Co-Mo/10% SiO2-Al2O3催化剂具有优良的加氢性能,在15 MPa、380℃、氢油比为1000、空速为0.6 h-1的反应条件下,其HDS和HDN数值均超过99%,产品中S含量小于10 μg/g,N含量小于2 μg/g,可以满足后续异构脱蜡等对原料的要求。

     

    Abstract: SiO2-Al2O3, with a mass content of 5%, 10% and 15%, was synthesized by using a Al(NO3)3-NaAlO2 double hydrolysis method, with surfactant Pluronic P123 as template and Si(OC2H5)4 as Si source. The Co-Mo/SiO2-Al2O3 hydrotreating catalysts for lubricating oil were then prepared by co-impregnation method and characterized by a series of techniques such as XRD, N2 sorption, Py-FTIR, NH3-TPD, H2-TPR, TEM and XRF. The results show that the SiO2-Al2O3 support containing 10% Si is provided with abundant moderate-strong acid sites and partially ordered mesoporous structure; MoS2 particles are uniformly dispersed on the SiO2-Al2O3 surface. Moreover, the Co-Mo/10%SiO2-Al2O3 catalyst exhibits high amount of Bronsted acid sites and type Ⅱ CoMoS active phase. The catalytic performance was evaluated in a high-pressure fixed-bed reactor, with second vacuum side distillate oil as the raw material oil. The results show that the Co-Mo/10%SiO2-Al2O3 catalyst exhibits high activity in hydrotreating and paraffins and cycloalkanes are the main components in product oil. Under 380℃, 15 MPa, a space velocity of 0.6 h-1, and a hydrogen to oil ratio of 1000, the HDS and HDN values over Co-Mo/10%SiO2-Al2O3 exceed 99%. Meanwhile, the contents of S and N in the product are less than 10 and 2 μg/g, respectively, which can meet the requirements on the raw materials for the subsequent isomerization dewaxing process.

     

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