Cr原位修饰粉煤灰基HZSM-5催化氧化CH2Cl2的性能研究

Catalytic oxidation performance of CH2Cl2 over in-situ Cr-modified fly ash-based HZSM-5

  • 摘要: 含氯挥发性有机物(CVOCs)的催化燃烧技术中,催化剂易发生氯中毒且深度氧化能力不足,是其工业化应用的关键瓶颈。以粉煤灰为原料耦合一步水热合成法原位制备了一系列Cr修饰的HZSM-5催化剂,采用XRD、UV-vis、XPS、N2吸-脱附、NH3-TPD、O2-TPD、H2-TPR等先进手段对催化剂物理化学性质进行了表征,并以二氯甲烷(CH2Cl2)为探针分子,系统研究不同Cr掺杂量和不同硅铝比对二氯甲烷的催化净化和抗氯中毒性能影响。结果表明,Cr原位修饰可有效抑制含氯副产物的生成且大幅提高HZSM-5分子筛对CVOCs氧化性能;1.2%Cr-HZSM-5(Si/Al摩尔比为50)具有较高表面酸性和氧化还原性,表现出较高的C—Cl键裂解和CH中间组分深度氧化能力,最高CO2选择性和较少的Cl沉积,350 ℃时二氯甲烷降解率、CO2和HCl产率分别可达85%、75%、60%,且未检测到Cl2及其他含氯副产物。本研究可为开发高效降解CVOCs的催化体系提供了理论依据与实验支撑。

     

    Abstract: In the catalytic combustion technology of chlorine-containing volatile organic compounds (CVOCs), the catalyst is prone to chlorine poisoning and exhibits insufficient deep oxidation capacity, which is the key bottleneck restricting its industrial application. In this study, a series of Cr-modified HZSM-5 catalysts were in-situ prepared by a one-step hydrothermal synthesis method using fly ash as the raw material. Advanced techniques such as XRD, UV-vis, XPS, N2 adsorption-desorption, NH3-TPD, O2-TPD, and H2-TPR were used to characterize the physical and chemical properties of the catalysts. Using dichloromethane(CH2Cl2) as the probe molecule, the effects of different Cr doping amounts and different Si/Al ratios on the catalytic purification and anti-chlorine poisoning were systematically studied. The results showed that in-situ Cr modification could effectively inhibit the formation of chlorine-containing by-products and significantly improve the oxidation performance of HZSM-5 zeolite for CVOCs. 1.2%Cr-HZSM-5 (Si/Al=50) had high surface acidity and redox properties, showing high ability for C-Cl bond cleavage and deep oxidation capacity toward CH intermediate components, with the highest CO2 selectivity and lower Cl deposition. At 350℃, the conversion rate of dichloromethane reached 85%; the yields of CO2 and HCl reached 75% and 60%, respectively; and no Cl2 or other chlorine-containing by-products were detected. This study can provide a theoretical basis and experimental support for the development of a catalytic system for efficient degradation of CVOCs.

     

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