碳纳米管的表面修饰对Co-Mo催化剂HDS性能影响的研究

碳纳米管的表面修饰对Co-Mo催化剂HDS性能影响的研究

  • 摘要: 采用程序升温脱附(TPD)、Boehm滴定以及质量滴定(Mass titration)等方法分析了多壁碳纳米管(MWCNT)经过浓硝酸改性处理前后的表面酸性和酸性分布;同时运用XRD技术研究了碳纳米管负载Co-Mo催化剂的表面物种和活性组分的分散;并在高压微型反应器中,以二苯并噻吩(DBT)为模型化合物,对碳纳米管负载的Co-Mo催化剂体系进行了加氢脱硫(HDS)活性评价,以期揭示碳纳米管的表面修饰对其负载Co-Mo催化剂HDS性能的影响。研究结果表明:MWCNT表面呈一定的碱性,通过浓硝酸化学修饰以后,反而呈现较强的酸性,并且随着酸处理时间的延长,表面的酸性进一步增加。如,M-MWCNT-6(酸化6h)表面总酸量为1.29×10-3mol/g,M-MWCNT-24(酸化24h)表面总酸量为2.46×10-3mol/g。酸改性提高了Co-Mo催化剂在MWCNT表面的分散程度,以致Co-Mo/MWCNT催化剂的HDS活性和选择性明显高于Co-Mo/γ-Al2O3催化体系。然而,Co-Mo/M-MWCNT-6的HDS活性以及选择性与Co-Mo/MWCNT相差不多,略有降低,但是仍比Co-Mo/γ-Al2O3催化体系的HDS活性高。Co-Mo/M-MWCNT-24催化剂的HDS活性降低很多,并且催化性能发生了很大改变,产物中出现了大量的副产物-1,2-二苯基乙烷。表明,深度酸化改性反而不利于提高碳纳米管负载Co-Mo催化体系的HDS活性。

     

    Abstract: Multi-walled carbon nanotubes (MWCNT) were modified by concentrated nitric acid and the effect on surface acidity, dispersion of Co-Mo catalysts on them, and hydrodesulfurization (HDS) activity were respectively characterized by temperature-programmed desorption (TPD) and Boehm and mass titration, XRD and a flow micro-high pressure reactor using dibenzothiophene (DBT) as the sulfur-containing model compound. It is found that MWCNT is slightly basic and that modified MWCNT shows strong acidity with total amount of acid for 6 and 24h modified samples, M-MWCNT-6 and M-MWCNT-24 being 1.29×10-3 and 2.46×10-3 mol/g respectively. The dispersion of Co-Mo catalyst on MWCNT is significantly improved after the modification. The activity and selectivity for HDS are apparently higher for Co-Mo/MWCNT than for Co-Mo/Al2O3. For the modified samples, however, a slight and a significant decrease of activity and selectivity for HDS is observed for both Co-Mo/M-MWCNT-6 and Co-Mo/M-MWCNT-24 with a large proportion of byproduct found for the latter, indicating that significant modification is unfavorable for HDS.

     

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