【作者】 李娟；

【导师】 邓文安； 王鸣；

【作者基本信息】 中国石油大学(华东) ， 化学工程（专业学位）， 2018， 硕士

【摘要】 将以镍剂试剂、聚乙烯吡咯烷酮以及分散溶剂制备的镍前驱体,和以仲钼酸铵、氨水以及硫化铵水溶液制备的钼前驱体通过自模板法合成纳微空心材料NiMoS₄;对NiMoS₄进行不同气体、不同温度条件下的退火还原处理,得到纳微空心结构材料NiMoS₃。采用TEM、SEM、XRD、FT-IR、UV、TGA、XPS、原子吸收、元素分析等测试方法对镍前驱体、钼前驱体以及制备的NiMoS₃进行表征。以克拉玛依常压渣油和青岛炼化催化裂化油浆为原料,对NiMoS₃空心材料作为分散型催化剂的加氢抑焦活性进行了评价。实验结果表明,在最优的制备条件下,制备镍前驱体的金属镍回收率为66.96%,钼前驱体的金属钼回收率为87.13%。通过自模板法制备的空心材料NiMoS₄在氢气气氛下300℃退火处理1 h后可以得到具有较好加氢抑焦活性的纳微空心材料NiMoS₃。制备的材料NiMoS₃微观结构为长340 nm左右,宽300 nm左右,壁厚10²0 nm的棱柱形空心结构;NiMoS₃中各元素在表面原子中Mo、Ni、S原子的百分率分别为23.4%、7.08%、64.26%,其余为C、N、O原子。在NiMoS₃所含的钼元素中,Mo⁴⁺离子占61.01%,Mo⁶⁺离子占34.72%。催化剂NiMoS₃的重油临氢热反应评价结果表明:氢气气氛、300℃退火处理后的NiMoS₃催化剂具有良好的催化活性,可以在反应中起到加氢抑焦作用。对比NiMoS₃催化剂与油溶性钼镍催化剂（钼与镍配比3:2）的加氢抑焦活性,在FCCS中NiMoS₃催化剂的催化活性优于油溶性钼镍;而在KLAR中油溶性钼镍的催化活性优于NiMoS₃催化剂。因此本文制备的催化剂NiMoS₃需要在加氢抑焦活性上进一步优化。更多还原

【Abstract】 Ni precursors prepared from nickel reagents,polyvinylpyrrolidone and dispersion solvents,and Mo precursor prepared from ammonium molybdate,aqueous ammonia,and ammonium sulfide solutions,respectively,were used to synthesize nano-hollow hollow materials NiMoS₄ through a self template process.Annealing and reducing treatment of NiMoS₄ under different gas and temperature conditions to obtain nano-micro hollow structural material NiMoS_3。The Ni precursor,Mo precursor and NiMoS₃ were characterized by TEM,SEM,XRD,FT-IR,UV,TGA,XPS,atomic absorption and elemental analysis.Using KLAR and FCCS as raw oil,the hydrogenation inhibition activity of NiMoS₃ hollow material as a dispersion catalyst was evaluated.The experimental results show that under the optimal preparation conditions,the recovery rate of nickel metal for the preparation of Ni precursor is 66.96%,and the molybdenum metal recovery rate of Mo precursor is 87.13%.NiMoS₃ hollow nano-materials with good hydrogenation inhibitory activity can be obtained after the hollow NiMoS₄prepared by the self template process is annealed in hydrogen atmosphere at 300℃for 1 hour.The prepared material NiMoS₃ microstructure is a prismatic hollow structure with a length of about 340 nm,a width of about 300 nm,and a wall thickness of 10-20 nm.The percentages of Mo,Ni and S atoms in the surface atoms of each element in NiMoS₃ are 23.4%and 7.08%,64.26%.the rest are C,N,O atoms.In NiMoS₃,the Mo⁴⁺ion content is 61.01%,and the Mo⁶⁺ion content is 34.72%.The evaluation results of the hydrothermal reaction of heavy oil catalyst NiMoS₃ show that the prepared NiMoS₃ catalyst has good catalytic activity and can play a role in hydrogenation inhibition in the reaction,and at the hydrogen atmosphere and the catalyst after annealing at 300℃,have the best hydrogenation inhibitory activity.Comparing the hydrogenation inhibition activity of NiMoS₃ catalyst and oil-soluble molybdenum-nickel catalyst（molybdenum to nickel ratio 3:2）,the catalytic activity of NiMoS₃ catalyst in FCCS is better than that of oil-soluble molybdenum nickel;The catalytic activity of oil-soluble molybdenum nickel in KLAR is better than that of NiMoS₃ catalyst.Therefore,the catalyst NiMoS₃ prepared in this article needs to be further optimized in the hydrogenation inhibition activity.更多还原