物理化学学报 >> 2012, Vol. 28 >> Issue (03): 661-666.doi: 10.3866/PKU.WHXB201112291

催化和表面科学 上一篇    下一篇

柠檬酸对Ni2P/TiO2-Al2O3催化剂加氢脱硫性能的影响

宋华1,2, 张永江1, 宋华林3, 代敏1   

  1. 1. 东北石油大学化学化工学院, 黑龙江大庆 163318;
    2. 东北石油大学, 石油与天然气化工省重点实验室, 黑龙江大庆 163318;
    3. 牡丹江医学院医学影像学院, 黑龙江牡丹江 157011
  • 收稿日期:2011-08-05 修回日期:2011-12-07 发布日期:2012-02-23
  • 通讯作者: 宋华 E-mail:songhua@nepu.edu.cn
  • 基金资助:

    黑龙江省科技厅(2009G0947-00)资助

Effect of Citric Acid on the Hydrodesulfurization Performance of Ni2P/TiO2-Al2O3 Catalyst

SONG Hua1,2, ZHANG Yong-Jiang1, SONG Hua-Lin3, DAI Min1   

  1. 1. College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang Province, P. R. China;
    2. Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, Heilongjiang Province, P. R. China;
    3. Department of Image School, Mudanjiang Medical University, Mudanjiang 157011, Heilongjiang Province, P. R. China
  • Received:2011-08-05 Revised:2011-12-07 Published:2012-02-23
  • Contact: SONG Hua E-mail:songhua@nepu.edu.cn
  • Supported by:

    The project was supported by the Heilongjiang Science and Technology Agency, China (2009G0947-00).

摘要: 采用溶胶-凝胶法制备了TiO2-Al2O3复合载体, 以柠檬酸(CA)为络合剂采用浸渍法制备了Ni2P负载的TiO2-Al2O3复合载体催化剂, 并用X射线衍射(XRD)、N2吸附比表面积测定、H2程序升温氢还原(H2-TPR)、程序升温氧化(TPO)、X射线光电子能谱(XPS)技术对催化剂的结构和性质进行了表征, 考察了CA/Ni 摩尔比对在Ni2P/TiO2-Al2O3催化剂上进行的二苯并噻吩(DBT)加氢脱硫(HDS)性能的影响. 结果表明: 适量的CA可以丰富催化剂的孔道, 提高催化剂的比表面积. 当n(CA)/n(Ni)=2:1 时, 催化剂的比表面积达到126.75 m2·g-1, 与不加CA时相比, 提高了57.05 m2·g-1. 调节n(CA)/n(Ni)能够改善活性相的分布, 改变活性相的种类; 引入CA使Ni和P前驱体的还原温度明显降低, 促进活性相Ni2P的生成, 一定程度上能够抑制催化剂表面炭的形成和沉积,提高其稳定性. n(CA)/n(Ni)=2:1时, 催化剂具有最好的加氢脱硫活性, 在360 °C, 3.0 MPa, 氢油比为500 (V/V),液时体积空速为2.0 h-1的条件下, 二苯并噻吩转化率为99.5%, 可将模拟油中硫含量由2%(w)降低到0.01%(w).

关键词: 加氢脱硫, 磷化二镍, 二氧化钛, 三氧化二铝, 柠檬酸, 络合剂

Abstract: A TiO2-Al2O3 complex support was prepared by the sol-gel method. Nickel phosphide catalyst, Ni2P/TiO2-Al2O3, with citric acid (CA) as a chelating agent, was prepared by impregnation. The catalyst was characterized by X-ray diffraction (XRD), BET specific surface area measurements, H2-temperature programmed reduction (TPR) and temperature programmed oxidation (TPO), and X-ray photoelectron spectroscopy (XPS). The effects of the molar ratio of CA to Ni on catalyst activity for hydrodesulfurization (HDS) of dibenzothiophene (DBT) were studied. Addition of an appropriate amount of CA into the catalyst can change the pores of the Ni2P/TiO2-Al2O3 catalyst, increasing the surface area. The specific surface area reached 126.75 m2·g-1 for n(CA)/n(Ni) of 2/1, an improvement of 57.05 m2·g-1 compared with the catalyst without CA. Regulating n(CA)/n(Ni) can improve the distribution of the active phase and change the active phase species. Addition of CA decreased the temperature required for reduction of nickel and the phosphorus precursor, as well as promoting the formation of the active phase. CA can limit the deposition of carbon on the catalyst surface to some extent, improving its stability. A molar ratio of n(CA)/n(Ni) of 2/1 was found to be optimal for the catalytic activity of the Ni2P/TiO2-Al2O3 catalyst prepared with CA as a chelating agent. At a reaction temperature of 360 °C, pressure of 3.0 MPa, hydrogen/oil ratio of 500 (V/V), and liquid hourly space velocity of 2.0 h-1, the HDS conversion of DBT was 99.5%, which can reduce the sulfur content of a model oil from 2% (w) to 0.01% (w).

Key words: Hydrodesulfurization, Nickel phosphide, Titanium dioxide, Al2O3, Citric acid, Chelating agent

MSC2000: 

  • O643.361