CIESC Journal ›› 2016, Vol. 67 ›› Issue (5): 1942-1948.DOI: 10.11949/j.issn.0438-1157.20151519

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Effects of temperature on adsorption mechanism and adsorption selectivity of C3H6 and C3H8 on MOF-74(Ni)

LIU Jiang, WU Yufang, XU Feng, XIAO Jing, XIA Qibin, LI Zhong   

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • Received:2015-10-08 Revised:2015-11-04 Online:2016-05-05 Published:2016-05-05
  • Supported by:

    supported by the Key Program of the National Natural Science Foundation of China(21436005).

温度对MOF-74(Ni)吸附分离丙烯丙烷机理和选择性的影响

刘江, 吴玉芳, 许峰, 肖静, 夏启斌, 李忠   

  1. 华南理工大学化学与化工学院, 广东 广州 510640
  • 通讯作者: 李忠
  • 基金资助:

    国家自然科学基金重点项目(21436005)。

Abstract:

MOF-74(Ni) was synthesized by solvothermal synthesis method and then characterized by PXRD and pore size analysis. Isotherms of C3H6 and C3H8 on the synthesized MOF-74(Ni) were measured at different temperatures. The temperature programmed desorption experiments were conducted to estimate the desorption activation energies of C3H6 and C3H8 on the MOF-74(Ni). IAST theory was applied to predict the adsorption selectivity of C3H6/C3H8 mixture. The effects of temperature on adsorption mechanism and adsorption selectivity were also discussed. Results showed that the as-synthesized MOF-74(Ni) had BET surfaces of 1306 m2·g-1, and its C3H6 adsorption capacity was up to 7.4 mmol·g-1 at 298 K. With rising temperature, the adsorption capacity of C3H8 on MIL-74(Ni) decreased sharply, while that of C3H6 decreased slightly, resulting in improvement of C3H6/C3H8 adsorption selectivity of MOF-74(Ni). It could be attributed to p-complexation bonding between C3H6 and MOF-74(Ni), which was stronger than the interaction of C3H8 with MOF-74(Ni). TPD results indicated that the desorption activation energy of C3H6 on MOF-74(Ni) was higher than that of C3H8, which were 68.92 kJ·mol-1 and 50.80 kJ·mol-1, respectively.

Key words: MOF-74(Ni), propylene, propane, adsorption isotherms, adsorption selectivity, temperature

摘要:

采用水热法成功制备了MOF-74(Ni),使用PXRD、孔径分析对材料进行了表征,测定了材料在不同温度下的C3H6和C3H8吸附等温线,应用程序升温脱附技术估算了脱附活化能,并使用IAST理论预测了材料对C3H6/C3H8二元体系的吸附选择性。讨论了温度对吸附机理和吸附选择性的影响。结果显示,MOF-74(Ni)的BET比表面积高达1306 m2·g-1。在298 K下,C3H6的吸附量高达7.4 mmol·g-1。随着温度升高,C3H8的吸附量大幅降低,而C3H6的吸附量下降程度较小,导致材料对C3H6/C3H8吸附选择性升高。当温度为328K时,MOF-74(Ni)对C3H6/C3H8二元气体混合物的吸附选择接近12。程序升温脱附的实验结果显示,C3H6在MOF-74(Ni)上的脱附活化能大于C3H8,分别为68.92 kJ·mol-1和50.80 kJ·mol-1。C3H6是通过与MOF-74(Ni)的不饱和金属位点Ni2+以p络合作用方式吸附,作用力较强,而C3H8与Ni2+之间的作用力较弱。根据吸附机理不同的特点,适当提高温度,将有助于提高MOF-74(Ni)吸附分离C3H6/C3H8混合物体系的吸附选择性。

关键词: MOF-74(Ni), 丙烯, 丙烷, 吸附等温线, 吸附选择性, 温度

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