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石油催化裂化再生烟气中氮氧化物脱除催化剂性能研究

Study on the performance of catalyst for removing nitrogen oxides from regenerated flue gas of petroleum catalytic cracking

  • 摘要:
    目的 石油催化裂化再生烟气中氮氧化物(NOx)需要采用氨气选择性催化还原(NH3-selective catalytic reduction, NH3-SCR)脱硝技术脱除。然而,传统的钒基催化剂低温活性差,易受到SO2的影响而发生中毒和失活,从而缩短其使用寿命,需要开发具有优异的低温活性和高抗SO2中毒性能的脱硝催化剂。
    方法 制备了一种新型Co掺杂的Cr2O3/Al2O3催化剂,研究了Co的掺杂量对Cr2O3/Al2O3催化剂的低温活性及抗SO2中毒能力的影响。
    结果 ①催化剂活性测试结果表明,掺杂Co可以显著提升Cr2O3/Al2O3催化剂的低温活性,其中,掺杂Co摩尔分数为20%的催化剂表现出最佳活性,当温度为116 ℃时,NOx转化率达到90%,且具有较好的抗SO2中毒能力;②催化剂表征结果表明,在催化剂中掺杂Co可增加酸性位点数量、Cr6+和表面吸附氧物种数目,从而提高选择性催化还原(selective catalytic reduction, SCR)反应速率。
    结论 所开发的经Co修饰的Cr基脱硝催化剂可实现低温脱硝,有利于石油催化裂化装置再生烟气中氮氧化物的脱除。

     

    Abstract:
    Objective The nitrogen oxides (NOx) in the regenerated flue gas of petroleum catalytic cracking need to be removed by NH3-selective catalytic reduction (NH3-SCR) denitration technology. However, the traditional vanadium-based catalysts exhibit poor low-temperature activity and are prone to poisoning and deactivation due to the influence of SO2, thereby shortening their service life. Therefore, it is necessary to develop denitration catalysts with excellent low-temperature activity and high SO2 poisoning resistance.
    Method A novel Co-doped Cr2O3/Al2O3 catalyst was prepared, and the effect of Co doping content on the low-temperature activity and SO2 poisoning resistance of the Cr2O3/Al2O3 catalyst was investigated.
    Result Firstly, catalytic activity test results showed that doping Co could significantly enhance the low-temperature activity of the Cr2O3/Al2O3 catalyst. Among them, the catalyst with a Co doping molar fraction of 20% exhibited the highest activity, which achieved a NOx conversion rate of 90% at 116 °C, along with good SO2 poisoning resistance. Secondly, catalyst characterization results indicated that doping Co into the catalyst increased the number of acidic sites, Cr6+ species, and surface-adsorbed oxygen species, thereby improving the selective catalytic reduction (SCR) reaction rate.
    Conclusion The developed Co-modified Cr-based denitration catalyst can achieve denitration at low-temperature, which is beneficial for the removal of nitrogen oxides in the regenerated flue gas of petroleum catalytic cracking units.

     

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