磷改性 Cu-SSZ-13 催化剂的抗水热老化性能研究

Anti-Hydrothermal Aging Property of Cu-SSZ-13 Catalyst by Phosphorus Modification

摘要

Cu-SSZ-13 催化剂是氨选择性催化还原(NH₃-SCR)氮氧化物的高效催化剂,然而水热稳定性不足严重制约了其实际应用与使用寿命. 为了提高 Cu-SSZ-13 催化剂的抗水热老化性能,采用浸渍法制备了一系列负载磷的 Cu-SSZ-13 催化剂. 通过催化反应评价系统、X 射线衍射(XRD)、比表面及孔径分析(BET)和 X 射线光电子能谱 (XPS)等表征深入分析了磷物种((NH₄)₂HPO₄、NH₄H₂PO₄ 和 H₃PO₄)对 Cu-SSZ-13 催化剂 NO 转化率及物理化学性质的影响. 结果表明:磷物种显著提高了 Cu-SSZ-13 催化剂在 400～550 ℃内的 NO 转化率,在 550 ℃时仍保持 85%以上；水热老化处理后,磷改性催化剂在 325～550 ℃内表现出更优的催化活性,其中负载 1.5%的 (NH₄)₂HPO₄、1%的 NH₄H₂PO₄ 和 1%的 H₃PO₄ 将 NO 转化率高于 90%的活性温度窗口扩宽 30～40 ℃. (NH₄)₂HPO₄ 改性可以保留催化剂更多的活性铜物种(Cu²⁺),而 NH₄H₂PO₄ 和 H₃PO₄ 改性能有效保护催化剂的孔隙结构. 此外,磷物种的引入能抑制水热老化过程中分子筛的脱铝,但其作用机制存在差异. 对于负载 (NH₄)₂HPO₄ 和 NH₄H₂PO₄ 的催化剂,磷化合物主要在催化剂表面与骨架外的铝形成磷酸铝物种；而负载 H₃PO₄ 的催化剂中,磷化合物则更倾向于直接与分子筛骨架铝相互作用,形成骨架硅铝磷酸盐界面及磷酸铝物种. 因此,磷改性是显著提高 Cu-SSZ-13 催化剂抗水热老化性能的有效策略.

Abstract

Cu-SSZ-13 catalyst is an efficient catalyst for ammonia selective catalytic reduction (NH₃-SCR) of NOx. However, the lack of hydrothermal stability seriously restricts its practical application and lifetime. In order to improve the anti-hydrothermal aging property of Cu-SSZ-13 catalyst, a series of phosphorus-loaded Cu-SSZ-13 catalysts were prepared by impregnation method. The effects of phosphorus species ((NH₄)₂HPO₄, NH₄H₂PO₄ and H₃PO₄) on the NO conversion rate and physicochemical properties of Cu-SSZ-13 catalyst were thoroughly analyzed by catalytic reaction evaluation system, X-ray diffraction (XRD), specific surface and pore size analysis (BET), and X-ray photoelectron spectroscopy (XPS). The results show that the NO conversion rate of Cu-SSZ-13 catalysts in the 400—550 ℃ range is markedly enhanced by phosphorus species, maintaining above 85% at 550 ℃. After hydrothermal aging treatment, the phosphorus-modified catalysts exhibit superior catalytic activity at 325—550 ℃. Among them, the loading of 1.5% (NH₄)₂HPO₄, 1% NH₄H₂PO₄ and 1% H₃PO₄ can widen the active temperature window of NO conversion rate higher than 90% by 30—40 ℃. (NH₄)₂HPO₄ modification can retain more active copper species (Cu²⁺) in the catalysts, while NH₄H₂PO₄ and H₃PO₄ modification can effectively protect the pore structure of the catalysts. In addition, the introduction of phosphorus species can inhibit the dealuminization of molecular sieves during hydrothermal aging, but the mechanisms of action are different. For catalysts loaded with (NH₄)₂HPO₄ and NH₄H₂PO₄, phosphorus compounds mainly react with extra-framework aluminum on the catalyst surface to form aluminum phosphate species. While for catalysts modified with H₃PO₄, phosphorus compounds tend to directly react with the framework aluminum, forming the framework silicoaluminophosphate interface and aluminum phosphate species. Therefore, phosphorus modification is an effective strategy to significantly enhance the anti-hydrothermal aging property of Cu-SSZ-13 catalyst.

关键词

氨选择性催化还原 / Cu-SSZ-13 / 磷改性 / 氮氧化物 / 抗水热老化性能 / 催化活性

Key words

ammonia selective catalytic reduction / Cu-SSZ-13 / phosphorus modification / NO_x / anti-hydrothermal aging property / catalytic activity

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基金资助

国家重点研发计划资助项目(2024YFC3712400)

国家自然科学基金资助项目(51921004)