石油学报(石油加工) ›› 2018, Vol. 34 ›› Issue (5): 882-890.doi: 10.3969/j.issn.1001-8719.2018.05.005

• 研究报告 • 上一篇    下一篇

掺杂金属的碳化硼氮的制备及其对柴油中含硫化合物的吸附

王延臻,李瑞杰,宋春敏,段红玲,高文銮,谢颂伟   

  1. 中国石油大学 化学工程学院, 山东 青岛 266580
  • 收稿日期:2017-08-14 修回日期:2017-09-14 出版日期:2018-09-25 发布日期:2018-12-10
  • 通讯作者: 王延臻,男,教授,博士,从事石油与天然气加工研究; E-mail: yanzhenw@upc.edu.cn E-mail:wyz3027@163.com
  • 基金资助:
    中国石油化工股份有限公司项目(115104)和中国石油大学(华东)研究生创新工程项目(YCX2017033)资助

Synthesis of Carbon and Metal-Doped Porous Boron Nitride: Adsorbents for Sulfur Removal From Diesel

WANG Yanzhen,LI Ruijie,SONG Chunmin,DUAN Hongling,GAO Wenluan,XIE Songwei   

  1. College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China
  • Received:2017-08-14 Revised:2017-09-14 Online:2018-09-25 Published:2018-12-10

摘要: 用三聚氰胺与硼酸合成了一种具有新形貌的介孔碳化硼氮(CBN)材料,并在其中掺杂Ag、Ni、Cu,合成出掺杂金属的碳化硼氮(M-CBN)。采用N2吸-脱附、SEM、XRD、NH3-TPD等手段对CBN与M-CBN进行了表征,考察了焙烧温度对CBN的影响及CBN与M-CBN对国V标准柴油中含硫化合物的吸附性能。结果表明,在890℃下焙烧制得的CBN比表面积高达1368 m2/g,3种掺杂不同金属的MCBN比表面积也均在1000 m2/g以上。CBN与M-CBN的形貌均为具有锋利边缘的类台阶状,且其孔径集中分布在3~10 nm之间。吸附过程为可自发进行的放热反应,15℃时的脱硫效果最佳。与CBN相比,M-CBN的总酸性位明显增多,吸附脱硫效果也更为优越,加入质量分数为1.25%的Ag-CBN吸附剂可使国V标准柴油中硫质量分数降至1 μg/g以下。Ag-CBN经4次再生循环使用后,脱硫率没有明显降低。

关键词: 碳化硼氮, 金属掺杂, 高比表面积, 吸附脱硫, 柴油 

Abstract: Novel mesoporous carbon and metal-doped boron nitride materials (CBN and M-CBN) were prepared by using melamine and boric acid as raw materials Multiple techniques, such as N2 adsorption-desorption, SEM, XRD and NH3-TPD, were applied to characterize the textural, morphology, acid properties and adsorptive desulfurization performance, respectively. The correlation between calcination temperature and the BET specific surface area of CBN was also investigated. The results show that when the calcination temperature is 890℃, the BET specific surface area of CBN reaches 1368 m2/g, at the same time its pore diameter intensively ranges from 3 to10 nm. Both CBN and M-CBN show a steplike shape with sharp edge in morphology. Sulfur compounds adsorption in CBN is an exothermal and spontaneous process. When adsorption temperature is 15℃, the CBN shows the best adsorption performance. The carbon and metaldoped boron nitride (M-CBN) displays a significantly higher amount of acid sites and exhibits enhanced adsorption performance for sulfur compounds in hydrogenated diesel than pure carbondoped boron nitride (CBN). In addition, it is the first time that a carbon and metaldoped mesoporous boron nitride are applied to adsorptive desulfurization. The addition of Ag to CBN with a mass fraction of 1.25% reduces the sulfur content in State V diesel to less than 1 μg/g. Ag-CBN is well regenerated by washing with toluene and heat treatment in nitrogen. The regenerated adsorbent still shows a good adsorption capacity after four regeneration cycles.

Key words: carbon-doped boron nitride, metal doping, high specific surface area, adsorptive desulfurization, diesel