石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (10): 58-65.

• 催化剂 • 上一篇    下一篇

磷改性ZSM-5及其对催化裂化增产丙烯的影响

侯硕旻1,段宏昌2,郭静静1,轩晓蝶1,毛佳薇1,李雪礼1,张琰图1   

  1. 1. 陕西省化学反应工程重点实验室,延安大学化学与化工学院
    2. 中国石油石油化工研究院兰州化工研究中心
  • 收稿日期:2022-02-28 修回日期:2022-04-09 出版日期:2022-10-12 发布日期:2022-09-23
  • 通讯作者: 李雪礼 E-mail:lzlixueli@163.com
  • 基金资助:
    陕西省自然科学基础研究计划;延安市科技局科技创新计划;延安大学博士科研启动项目;延安大学研究生教育创新计划项目;延安大学大学生创新创业训练计划项目

EFFECT OF PHOSPHORUS MODIFICATION ON THE ZSM-5 ZEOLITE FOR INCREASING PROPYLENE PRODUCTION IN FCC UNIT


  • Received:2022-02-28 Revised:2022-04-09 Online:2022-10-12 Published:2022-09-23
  • Contact: xueli li E-mail:lzlixueli@163.com

摘要: 对催化裂化(FCC)催化剂/助剂进行功能改性是提高丙烯产量、助力炼油厂转型升级的一种简单有效的方法。制备了经过碱处理和不同含量磷改性的ZSM-5分子筛[xP/A/ZSM-5,x表示分子筛磷负载量(以P2O5质量分数计),%],将其用于FCC增产丙烯。采用X射线衍射、透射电镜、31P固体核磁共振和X射线光电子能谱等表征方法对改性样品的结构、酸性和磷存在形态进行表征,并对其在FCC过程中增产丙烯的性能进行研究。结果表明,所有改性后ZSM-5作用下的丙烯收率均优于改性前ZSM-5分子筛,这与孔体积减小和酸度变化有关。在测试的助剂中,8.0P/A/ZSM-5样品的催化性能最好,丙烯收率为8.62%。对磷与ZSM-5分子筛相互作用机理的研究表明,磷能与骨架铝和非骨架铝相互作用形成AlPO4物种,并在磷改性分子筛表面检测到了AlPO4物种。

关键词: ZSM-5分子筛, 磷改性, 催化裂化, 丙烯, 作用机制

Abstract: Direct functional modification of fluid catalytic cracking (FCC) catalyst additives is a simple and effective method for increasing propylene production. ZSM-5 modified by alkali and different content of phosphorus named XP/A/ZSM-5 was prepared for increasing propylene production in FCC unit,in which x means the loading amount of phosphorus (calculated by the mass fraction of P2O5,%) . The structure, acidity and phosphorus forms of modified samples were characterized by XRD, TEM, 31P NMR and XPS. The performance of increasing propylene production in FCC process was studied. The results show that the propylene yield of all phosphorus modified samples is better than that of ZSM-5, which is related to the decrease of pore volume and acidity. Among the tested additives, 8.0 P/A/ZSM-5 sample had the best catalytic performance, and the yield of propylene was 8.62%. The interaction mechanism of phosphorus and ZSM-5 zeolites showed that phosphorus could interact with framework aluminum and non-framework aluminum to form AlPO4 species which were detected on the surface of phosphorus modified zeolites.

Key words: ZSM-5 zeolite, phosphorus modification, catalytic cracking, propylene, interaction mechanism