Macroporous Al2O3 with three-dimensionally interconnected structure: Catalytic performance of hydrodemetallization for residue oil
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摘要: 采用相分离技术制备了具有三维贯通大孔结构的Al2O3载体,载体的大孔尺寸为250 nm,比表面积174 m2/g,具有21 nm及250 nm集中的双重孔分布,抗压强度达到16.5 N/mm。采用该载体制备的渣油加氢脱金属催化剂仍然保持与载体接近的双峰孔分布、三维贯通大孔结构及较大的抗压强度等特性,Ni、Mo金属组分在载体表面分散均匀。催化剂的片层状活性相的长度为3−10 nm,堆垛层数1−7层,其中,大于4层的活性相分布约占40%,形成非均匀形态的活性相结构。与现有工业催化剂相比,三维贯通大孔渣油加氢脱金属催化剂的脱金属率、脱硫率及脱残炭率分别提高6.2%、6.0%及6.8%,孔结构、表面性质、活性相结构及其协同作用是三维贯通大孔催化剂具有优异催化性能的主要原因。Abstract: Three-dimensionally interconnected macroporous (3DM) Al2O3 was prepared by phase separation. Macropore size of the obtained Al2O3 is 250 nm with a bimodal pore distribution (at about 21 and 250 nm, respectively) and the BET specific surface area of 174 m2/g, as well as the crushing strength of 16.5 N/mm. Ni and Mo on the 3DM catalyst are uniformly dispersed on the surface of the support. The active phases of sulfurized catalyst possess length of 3−10 nm and stacking layers of 1−7. The stacking distribution of active phase more than 4 layers is about 40%, forming a non-uniform active phase structure. Compared with the industrial catalysts, the hydrodemetallization (HDM) rate, hydrodesulfurization (HDS) rate and hydrodecarbonization (HDCCR) rate of the 3DM catalyst increase by 6.2%, 6.0% and 6.8%, respectively. The pore structure, surface properties, active phase structure and their synergistic effect may be the main reasons for the excellent catalytic performance of the 3DM catalyst.
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Key words:
- 3D-interconnected /
- macroporous alumina /
- hydrodemetallization /
- residue oil
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图 2 3DM Al2O3载体、3DM催化剂和参比剂载体的显微照片3DM Al2O3载体的光学显微照片;(b)、(c)3DM Al2O3载体的SEM照片;(e)3DM催化剂的SEM照片;(f) 参比剂所用Al2O3载体的SEM照片
Figure 2 Micrographs of 3DM Al2O3 support, 3DM catalyst and reference support (a): Optical image of 3DM Al2O3 support; (b) and (c): SEM images of 3DM Al2O3 support; (e): SEM image of 3DM catalyst; (f): SEM image of reference support
表 1 载体与催化剂的物理吸附及抗压强度测试
Table 1 Results of physical adsorption and crushing strength of 3DM support 3DM catalyst and reference catalyst
Macroporous support Macroporous catalyst Reference support Reference catalyst Specific surface area/(m2·g−1) 174 150 169 153 Pore volume/(m3·g−1) 1.21 0.92 0.85 0.67 Crushing strength/(N·mm−1) 16.5 17.5 16.2 16.8 表 2 3DM催化剂与参比剂的酸强度分布
Table 2 Acid strength distributions of 3DM catalyst and reference catalyst
Weak acid(160−250 ℃)/% Medium acid(250−450 ℃)/% Strong acid(> 450 ℃)/% 3DM catalyst 67.35 27.15 5.50 Reference catalyst 63.74 28.90 7.36 表 3 3DM催化剂与参比剂的渣油加氢催化性能评价
Table 3 Evaluation results of catalytic performance of 3DM catalyst and reference catalyst for residue hydrogenation
Compositions w/% HDM/% HDS/% CCR/% MoO3 NiO Ni+V Ni V Fe* 3DM catalyst 11.3 2.7 64.3 52.4 68.8 − 48.9 33.5 Reference catalyst 11.4 2.9 58.1 48.9 61.7 − 42.9 26.7 * removal of Fe was not investigated because of the introduction of Fe into the products due to pipeline corrosion -
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