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摘要: 以Pluronic P123作结构导向剂,采用Al(NO3)3-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。
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关键词:
- SiO2-Al2O3载体 /
- Co-Mo催化剂 /
- 润滑油 /
- 加氢处理
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.-
Key words:
- SiO2-Al2O3 support /
- Co-Mo catalyst /
- lubricating oil /
- hydrotreating
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表 1 不同硅含量载体及催化剂的孔结构性质
Table 1 Textural properties of SiO2-Al2O3 supports with different Si contents
Support ABET /(m2·g-1) Pore volume v/(cm3·g-1) APD /nm γ-Al2O3 262 0.55 8.97 5%SiO2-Al2O3 395 1.03 10.65 10%SiO2-Al2O3 406 1.41 14.41 15%SiO2-Al2O3 372 1.36 15.31 表 2 不同硅含量载体中的酸分布
Table 2 Distribution of acid sites in SiO2-Al2O3 supports with different Si contents
Support Total acidity /% Weak acidity /% Medium strong acidity /% Strong acidity /% γ-Al2O3 100 36 52 12 5%SiO2-Al2O3 82 28 54 18 10%SiO2-Al2O3 65 16 61 23 15%SiO2-Al2O3 75 21 58 21 表 3 不同硅含量催化剂的孔结构性质
Table 3 Textural properties of various catalysts with different Si contents
Catalyst ABET /(m2·g-1) Pore volume v /(cm3·g-1) APD /nm Co-Mo/5%SiO2-Al2O3 343 0.68 7.7 Co-Mo/10%SiO2-Al2O3 363 0.76 8.4 Co-Mo/15%SiO2-Al2O3 316 0.72 9.1 表 4 Co-Mo/10%SiO2-Al2O3催化剂的XRF分析
Table 4 XRF results of Co-Mo/10%SiO2-Al2O3 catalyst
Compound Al2O3 SiO2 MoO3 CoO Composition w/% 62.6 9.8 19.5 8.1 表 5 原料油性质
Table 5 Properties of raw oil
Properties Second vacuum side distillate oil d20 /(g·cm-3) 0.891 Kinematic viscosity /(mm2·s-1) 6.268 Sulphur content /(mg·kg-1) 756 Nitrogen content /(mg·kg-1) 789 Saturate /% 68.20 Aromatics /% 24.43 Colloid and asphaltene /% 7.37 表 6 生成油的组成
Table 6 Composition of product oil over Co-Mo/10%SiO2-Al2O3
Hydrocarbon fractions Content w/% Paraffin 51.2 Cycloalkane 38.2 Mononuclear aromatics 4.1 Double ring aromatics 0.8 Three ring aromatics 0.1 Four ring aromatics 0.1 Aromatics 5.5 Total 100 表 7 原料油和生成油的馏程分布
Table 7 Distillation range of raw oil and product oil over Co-Mo/10%SiO2-Al2O3
Project Distillation range t /℃ raw material oil product oil ASTM D86 - - IBP 354.9 210.8 5% 378.4 229.6 10% 390.7 262.2 20% 404.3 309.4 30% 411.2 343.5 50% 421.4 402.2 70% 426.7 419.3 80% 430.3 434.2 90% 441.7 453.2 FBP 459.5 477.7 -
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