物理化学学报 >> 2006, Vol. 22 >> Issue (09): 1116-1120.doi: 10.3866/PKU.WHXB20060916

研究论文 上一篇    下一篇

杂原子Y分子筛的二次合成及其吸附脱硫性能

唐克;宋丽娟;段林海;李秀奇;桂建舟;孙兆林   

  1. (兰州大学化学化工学院, 兰州 730000; 辽宁石油化工大学石油化工学院, 辽宁 抚顺 113001)
  • 收稿日期:2006-03-26 修回日期:1900-01-01 发布日期:2006-09-04
  • 通讯作者: 孙兆林 E-mail:zlsun@lnpu.edu.cn

Deep Desulfurization by Selective Adsorption on Heteroatom Zeolite Prepared by Secondary Synthesis

TANG Ke;SONG Li-Juan;DUAN Lin-Hai;LI Xiu-Qi;GUI, Jian-Zhou;SUN Zhao-Lin   

  1. (College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China; College of Petrochemical Engineering, Liaoning University of Petroleum & Chemical Technology, Fushun 113001, P. R. China)
  • Received:2006-03-26 Revised:1900-01-01 Published:2006-09-04
  • Contact: SUN Zhao-Lin E-mail:zlsun@lnpu.edu.cn

摘要: 采用液-固相同晶取代反应制备了骨架含Ga的Y型分子筛, 并对其吸附脱硫性能进行了研究. 在室温, 空速为7 h−1的条件下, 镓化Y型分子筛([Ga]AlY)处理噻吩、四氢噻吩、4,6-二甲基二苯并噻吩(4,6-DMDBT)正壬烷溶液(硫含量500 μg•g−1), 每克吸附剂吸附硫的量分别为7.7、17.4、14.5 mg. 采用密度泛函理论(DFT)中的广义梯度近似方法(GGA)计算各分子中硫原子上的电荷数, 噻吩中硫原子的电荷数为−0.159, 而4,6-DMDBT和四氢噻吩分别为−0.214、0.298. 四氢噻吩和4, 6-DMDBT中硫原子上的电子密度大于噻吩中硫原子上的电子密度, 这就使得四氢噻吩和4,6-DMDBT中的硫原子与吸附位间的作用会远大于噻吩中的硫原子与吸附位间的作用, 吸附容量必然会大很多. 采用[Ga]AlY处理抚顺石油二厂的催化裂化汽油(硫含量:299 μg•g−1), 每克吸附剂处理2.1 mL汽油时, 处理后汽油的硫含量为54.8 μg•g−1, 说明[Ga]AlY对汽油脱硫有一定的效果.

关键词: 同晶取代, 杂原子分子筛, 吸附脱硫, 模拟燃料, DFT

Abstract: Gallium atoms had been introduced into the framework of Y zeolite by treatment of zeolites with an aqueous solution of ammonium hexafluoro gallate. At ambient conditions and space velocity of 7 h−1, desulfurization of various model fuel, containing about 500 μg•g−1 sulfur was studied over the synthesized Y zeolite. Every gram adsorbent could adsorb 7.7, 17.4, 14.5 mg sulfur from thiophene, tetrahydrothiophene, 4,6-dimethyldibenzothiophene (4,6-DMDBT), respectively. The charge on S atom of thiophene, 4,6-DMDBT, and tetrahydrothiophene, calculated by using density functional theory (DFT), were −0.159, −0.214, and −0.298 respectively, implying that the S—M bond between the adsorption site and thiophene was much weaker than that between the adsorption site and tetrahydrothiophene or 4,6-DMDBT. The synthesized Y zeolites were evaluated for the adsorptive desulfurization of the FCC gasoline (sulfur content:299 μg•g−1) supplied by the No.2 Refinery in Fushun. After 2.1 mL gasoline being treated in one gram adsorbent, the sulfur content was 54.8 μg•g-1.

Key words: Isomorphous substitution, Heteroatom Zeolite, Adsorption desulfurization, Model Fuel, DFT