催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (9): 1586-1593.DOI: 10.3724/SP.J.1088.2012.20330

• 研究论文 • 上一篇    下一篇

TiO2-Al2O3 的水热法合成及其负载的 NiMoP 催化剂上 FCC 柴油加氢脱硫性能

洪伟1,3, 刘百军1,a, 王宏宾2, 陈玉1,b   

  1. 1中国石油大学 (北京) 化学工程学院, 重质油国家重点实验室, CNPC 催化重点实验室, 北京 102249; 2沈阳三聚凯特催化剂有限公司, 辽宁沈阳 110144; 3中国石油工程建设公司北京设计分公司, 北京 100101
  • 收稿日期:2012-04-19 修回日期:2012-06-21 出版日期:2012-09-11 发布日期:2012-09-11

Hydrothermal Synthesis of TiO2-Al2O3 Composite Oxide and Catalytic Performance of Its Suppored NiMoP for Hydrodesulfurization of FCC Diesel

HONG Wei1,3, LIU Baijun1,a, WANG Hongbin2, CHEN Yu1,b   

  1. 1State Key Laboratory of Heavy Oil Processing, the Key Laboratory of Catalysis of CNPC, Faculty of Chemical Engineering, China University of Petroleum, Beijing 102249, China; 2Shenyang Sanjukaite Catalyst Co., Ltd., Shenyang 110144, Liaoning, China; 3China Petroleum Engineering &Construction Corporation Beijing Engineering Branch, Beijing 100101, China
  • Received:2012-04-19 Revised:2012-06-21 Online:2012-09-11 Published:2012-09-11

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摘要： 采用水热法制备了复合氧化物 TiO2-Al2O3, 研究了水热温度、反应物浓度、聚乙二醇 (PEG) 平均分子量和浓度对所制样品结构和织构性质的影响, 并用 X 射线衍射、N2 吸附-脱附、热重-差热分析、NH3 程序升温脱附、吸附吡啶的红外光谱和程序升温还原技术对 TiO2-Al2O3 及其负载的 NiMoP 催化剂进行了表征, 在中压固定床微反装置上考察了催化剂上 FCC 柴油的加氢脱硫性能. 结果表明, 随着水热温度、反应物浓度、PEG 分子量和浓度的提高, 所制 TiO2-Al2O3 复合氧化物的比表面积和孔体积均有所提高, 在优化的制备条件下分别可高达 266 m2/g 和 0.58 cm3/g, 其负载的 NiMoP 催化剂的比表面积也高达 175 m2/g, 且其酸性较弱, 以 L 酸为主. 由于 NiMoP/TiO2-Al2O3 催化剂中 TiO2 的存在降低了活性组分与载体间的强相互作用, 使其催化 FCC 柴油加氢脱硫活性比 NiMoP/Al2O3 催化剂的高.

关键词: 二氧化钛, 氧化铝, 复合氧化物, 水热合成, 聚乙二醇, 催化裂化柴油, 加氢脱硫

Abstract:  The TiO2-Al2O3 composite oxide was synthesized by the hydrothermal method. The effects of hydrothermal temperature, reactant concentration, average molecular mass of polyethylene glycol, and polyethylene glycol concentration on the structural and textural properties of TiO2-Al2O3 composite oxide were studied. The composite oxide and NiMoP/TiO2-Al2O3 catalyst were characterized by powder X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy (SEM), thermogravimetric and differential thermal analysis (TG-DTA), NH3 temperature-programmed desorption (NH3-TPD), pyridine adsorption in situ infrared spectroscopy (Py-FTIR), and H2 temperature-programmed reduction (H2-TPR). The catalytic performance of the catalyst for hydrodesulfurization of fluid catalytic cracking (FCC) diesel was evaluated in a fixed-bed reactor with medium pressure. The results show that both specific surface area and pore volume of the TiO2-Al2O3 composite oxide increased with increasing hydrothermal temperature, reactant concentration, average molecular mass of polyethylene glycol, and polyethylene glycol concentration. Under the optimum conditions, the specific surface area and pore volume of the TiO2-Al2O3 composite oxide could reach up to 266 m2/g and 0.58 cm3/g, respectively. The specific surface area of NiMoP/TiO2-Al2O3 catalyst also reached as high as 175 m2/g. The results of NH3-TPD and Py-FTIR show that NiMoP/TiO2-Al2O3 catalyst has a weak acidity wherein Lewis acid is dominative. The NiMoP/TiO2-Al2O3 catalyst has higher desulfurization activity due to the existence of TiO2, which can decrease the strong interaction between the active phase and the support. Hydrodesulfurization activity for FCC diesel over NiMoP/TiO2-Al2O3 catalyst is thus 5.4% higher than that on the NiMoP/Al2O3 catalyst.

Key words: titania, alumina, composite oxide, hydrothermal synthesis, polyethylene glycol, fluid catalytic cracking diesel, hydrodesulfurization