制备条件对Cu-SSZ-13分子筛的形貌及其氨选择性催化还原脱硝性能的影响

Effect of preparation conditions on the morphology of Cu-SSZ-13 zeolites and their performance in the selective catalytic reduction of NOx by NH3

  • 摘要: 采用传统水热法合成SSZ-13分子筛,铜离子交换法制备Cu-SSZ-13分子筛催化剂,用于氨选择性催化还原(NH3-SCR)脱硝,研究了有机模板剂(OSDA)用量、硅源、铝源、水硅比、硅铝比以及老化时间等制备参数对Cu-SSZ-13分子筛形貌、晶粒大小、酸性、Cu2+位点以及NH3-SCR催化性能的影响。结果表明,在一定范围内,SSZ-13分子筛的硅铝比越高,其晶粒越大,所负载的活性铜含量越低,NH3-SCR催化活性也越差。以硅溶胶为硅源、硫酸铝为铝源所合成的SSZ-13分子筛晶粒较小,结晶度最高,所得到的Cu-SSZ-13催化剂的NH3-SCR活性也最好。较高的水硅比所合成的分子筛晶粒较大,而增加模板剂的用量有利于提高SSZ-13分子筛的结晶度,降低其晶粒尺寸。适当延长老化时间,能降低SSZ-13分子筛晶粒尺寸,提升Cu-SSZ-13的NH3-SCR催化活性。其中,Si/Al比为10、硅溶胶为硅源、硫酸铝为铝源、OSDA/Si比为0.4、水硅比为88、老化2 h得到的Cu-SZ-A10催化剂最优,在240000 h−1的高空速下,200 ℃时NO转化率达60%,且在中高温区NO转化率保持为100%。该工作对SSZ-13分子筛形貌的调控以及高性能NH3-SCR脱硝催化剂的制备具有重要的参考价值。

     

    Abstract: SSZ-13 zeolites were synthesized by conventional hydrothermal method and the Cu-SSZ-13 zeolite catalysts were then prepared by Cu ion-exchange and used in the selective catalytic reduction of NOx with NH3 (NH3-SCR); the effect of various preparation parameters including the organic template agent (OSDA) dosage, silicon source, aluminum source, H2O/Si ratio, Si/Al ratio and aging time on the morphology, crystal size, acidity, state of Cu2+ sites and the catalytic performance of Cu-SSZ-13 in NH3-SCR were investigated. The results indicate that silica sol (JN25) and Al2(SO4)3 are appropriate as the silicon and aluminum sources, respectively, to prepare SSZ-13 zeolites with small crystals, high crystallinity and high activity in NH3-SCR. With the increase of Si/Al ratio, the crystal size of SSZ-13 increases and the copper content loaded on Cu-SSZ-13 decreases, leading to the degradation of NH3-SCR activity. A high H2O/Si ratio of 88 is conducive to forming larger SSZ-13 crystals, whilst increasing the OSDA dosage is beneficial to improving the crystallinity, reducing the crystal size, and accordingly enhancing the catalytic activity of Cu-SSZ-13 in NH3-SCR. In addition, a relatively longer aging time can also reduce the crystal size and raise the catalytic activity of Cu-SSZ-13. In particular, the Cu-SZ13-A10 zeolite catalyst synthesized with a Si/Al ratio of 10 (with the gel composition of 1SiO2 : 0.01Al2(SO4)3 : 0.3NaOH : 0.4SDA : 88H2O; JN25 as silicon source and aging for 2 h) exhibits high activity in NH3-SCR; under a high GHSV of 240000 h−1, the NO conversion reaches 60% at 200 ℃ and keeps at 100% in the moderate-high temperature range. These results should be useful for the regulation of SSZ-13 zeolite morphology and the preparation of high efficient Cu-SSZ-13 catalysts for NH3-SCR.

     

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