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    MnOx/SFCCC催化剂室温催化氧化甲醛:失活与再生

    Catalytic oxidation of formaldehyde at room temperature over MnOx/SFCCC catalyst: deactivation and regeneration

    • 摘要: 针对锰基催化剂室温催化氧化甲醛过程中易失活的问题,提出以废弃FCC催化剂(Spent fluid catalytic cracking catalyst,SFCCC)为载体,采用原位生长法制备了MnOx/SFCCC催化剂,考察了该催化剂在连续反应过程中的失活原因及50-250 ℃热再生后的性能恢复效果。其中200 ℃热再生后的催化剂性能恢复最佳,其活性可在10 h内恢复至95%,在连续四次“反应-再生”循环后甲醛脱除率仍保持在60%以上。BET与SEM结果表明,新鲜催化剂比表面积与孔容分别为154 m2·g−1和 0.191 cm3·g−1,失活后催化剂表面出现小颗粒团聚现象且比表面积显著下降,比表面积和孔容分别降至90 m2·g−1和0.141 cm3·g−1,200 ℃再生后则恢复至130 cm3·g−1和0.185 cm3·g−1。XPS、O2-TPD、H2-TPR分析发现,失活伴随着Mn3+物种还原及表面还原性氧物种的消耗。结合FTIR、TPO与TG进一步证实,催化剂失活主要由甲酸盐为主的含碳中间体可逆覆盖活性位点所致,在200 ℃温和加热可以实现催化剂的再生。

       

      Abstract: To address the deactivation of Mn-based catalysts during the catalytic oxidation of formaldehyde at room temperature, a MnOx/SFCCC catalyst was prepared via an in-situ growth method using spent fluid catalytic cracking catalyst (SFCCC) as the support. The causes of catalyst deactivation during continuous operation and the performance recovery after thermal regeneration at 50-250 °C were systematically investigated. Among the regeneration temperatures examined, the catalyst regenerated at 200 °C exhibited the best recovery performance, with its activity restored to 95% within 10 h. After four consecutive reaction–regeneration cycles, the formaldehyde removal efficiency still remained above 60%. BET and SEM results showed that the fresh catalyst possessed a specific surface area of 154 m2·g−1 and a pore volume of 0.191 cm3·g−1. After deactivation, small-particle agglomeration appeared on the catalyst surface, accompanied by a significant decrease in textural properties, with the specific surface area and pore volume dropping to 90 m2·g−1 and 0.141 cm3·g−1, respectively. After regeneration at 200 °C, these values recovered to 130 m2·g−1 and 0.185 cm3·g−1, respectively. XPS, O2-TPD, and H2-TPR analyses revealed that catalyst deactivation was associated with the reduction of Mn3+ species and the consumption of surface reducible oxygen species. FTIR, TPO, and TG further confirmed that the deactivation mainly resulted from the reversible coverage of active sites by carbon-containing intermediates, predominantly formate species, and that mild heating at 200 °C could effectively regenerate the catalyst.

       

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