钙改性HZSM-5分子筛对油页岩热解特性的影响研究

Effect of Ca modified HZSM-5 zeolites on catalytic pyrolysis of oil shale

  • 摘要: 采用热重质谱红外光谱(TG-MS-FTIR)联用技术和管式热解炉,探究了Ca改性前后HZSM-5分子筛对油页岩热解的催化行为,并采取BET、NH3-TPD、TG手段对分子筛进行表征。结果表明,改性前后的HZSM-5均可以显著提高C1−4脂肪烃类产物的产量,降低其析出温度。Ca改性后的HZSM-5可以降低CO2的产量。对页岩油的分析表明,改性后的HZSM-5可以提高页岩油产量,并且有效降低页岩油中脂肪链长度。但是对芳构化促进作用更强。分子筛中Brönsted酸位点对脂肪烃催化效果明显,Lewis酸位点有利于芳构化反应的发生。

     

    Abstract: The catalytic behaviors of Ca-modified HZSM-5 during oil shale pyrolysis process were investigated in a tubular rector and by TG-MS-FTIR. The physicochemical properties of the molecular sieve were characterized by BET, NH3-TPD, and TG. The results show that the molecular sieve can significantly increase yields of C1−4 aliphatic hydrocarbons and reduce their evolution temperatures. After modified, Ca/HZSM-5 can reduce yields of CO2, increase yields of shale oil and decrease lengths of aliphatic chains in shale oil. But Ca/HZSM-5 has a strong catalytic effect on aromatization. Brönsted acid sites have an obvious catalytic effect on aliphatic hydrocarbons, while Lewis acid sites are more targeted at aromatization process of pyrolysis products.

     

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