物理化学学报 >> 2011, Vol. 27 >> Issue (07): 1737-1742.doi: 10.3866/PKU.WHXB20110728

催化和表面科学 上一篇    下一篇

B助剂对Ni2P/SBA-15催化剂结构及其加氢脱硫性能的影响

赵鹏飞, 季生福, 魏妮, 马倩, 刘辉, 李成岳   

  1. 北京化工大学, 化工资源有效利用国家重点实验室, 北京 100029
  • 收稿日期:2010-12-29 修回日期:2011-04-05 发布日期:2011-06-28
  • 通讯作者: 季生福 E-mail:jisf@mail.buct.edu.cn
  • 基金资助:

    国家基础研究重大项目计划(973) (2006CB202503)基金资助

Effect of Boron Promoter on the Structure and Hydrodesulfurization Activity of Ni2P/SBA-15 Catalysts

ZHAO Peng-Fei, JI Sheng-Fu, WEI Ni, MA Qian, LIU Hui, LI Cheng-Yue   

  1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China
  • Received:2010-12-29 Revised:2011-04-05 Published:2011-06-28
  • Contact: JI Sheng-Fu E-mail:jisf@mail.buct.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2006CB202503).

摘要:

以介孔分子筛SBA-15为载体, 磷酸氢二铵为磷源, 硝酸镍为镍源, 硼酸为硼源, 采用共浸渍法制备了B-Ni2P/SBA-15催化剂前驱体, 然后采用程序升温氢气还原法, 制备了nP/nNi=0.8, B含量为0.35%-2.10%(w)的一系列B-Ni2P/SBA-15催化剂. 用X射线衍射(XRD)、N2吸附脱附、透射电子显微镜(TEM)和氨气程序升温脱附(NH3-TPD)等表征技术对催化剂的结构进行了研究, 以1%(w)二苯并噻吩(DBT)/十氢萘溶液为模型化合物, 在微型固定床反应器上对催化剂的加氢脱硫(HDS)性能进行了评价. 结果表明, B-Ni2P/SBA-15催化剂仍具有介孔结构, Ni2P为主要的活性物相. 适量B助剂的加入可促使Ni2P晶粒减小, 催化剂比表面积增加. 此外, 随着B含量的增加, B-Ni2P/SBA-15催化剂的总酸量也增加. 当反应压力为3.0 MPa, 反应温度由300 ℃升高至360 ℃时, B含量对Ni2P/SBA-15催化剂活性有明显的影响, B含量为1.40%(w)的B-Ni2P/SBA-15催化剂加氢脱硫活性最高. B-Ni2P/SBA-15催化剂上二苯并噻吩的加氢脱硫的反应机理以直接脱硫为主.

关键词: 加氢脱硫, SBA-15, Ni2P, 二苯并噻吩,

Abstract:

The catalyst precursors of B-Ni2P/SBA-15 were synthesized by co-impregnation using (NH4)2HPO4 as the source of phosphorus, Ni(NO)3 as the source of nickel and H3BO3 as the source of boron. The B-Ni2P/SBA-15 catalysts with an initial P/Ni molar ratio of 0.8 and a boron content from 0.35% to 2.10%(w) were prepared by temperature-programmed reduction in a H2 flow. The structure of the catalysts was characterized by X-ray diffraction (XRD), N2 adsorption-desorption, transmission electron microscopy (TEM) and NH3 temperature-programmed desorption (NH3-TPD). The catalytic performances of hydrodesulfurization (HDS) were evaluated in a fixed-bed microreactor using dibenzothiophene (DBT) as a model compound. The results showed that the B-Ni2P/SBA-15 catalysts still retained mesoporous structure. The Ni2P phase was mainly active phases in all the catalysts. The proper addition of boron reduced the Ni2P active phases but increased the specific surface area of the catalysts. The amount of acid in B-Ni2P/SBA-15 also increased with addition of boron. When the reaction temperature was increased from 300 to 360 ℃, the HDS conversion of DBT over the catalyst clearly improved with an increase in the content of boron. The B-Ni2P/SBA-15 catalyst with a boron content of 1.40%(w) had the best catalytic activity. The mechanism of the HDS of DBT consisted of main direct desulfurization (DDS) over the B-Ni2P/SBA-15 catalysts.

Key words: Hydrodesulfurization, SBA-15, Ni2P, Dibenzothiophene, Boron

MSC2000: 

  • O641