制备方法对磷锆复合改性ZSM-5分子筛及其催化裂化性能的影响

在组合使用烘干、焙烧、水热老化处理的不同方法制备了磷改性ZSM-5分子筛的基础上，引入金属组分锆制备了磷锆复合改性ZSM-5分子筛系列试样（标记为PHZ-Z 5，PBZ-Z 5，PLZ-Z 5），并以复合改性分子筛为活性组分制备了催化裂化助剂，使用XRD，BET，NH3-TPD，XPS等方法对经水热老化处理后的磷锆复合改性后分子筛进行了表征，在先进的催化裂化催化剂评价装置（ACE）上，考察评价了不同改性方法制备所得催化助剂对重油催化裂化生产丙烯的影响。结果表明:在连续依次经烘干、焙烧、水热老化处理所得磷改性ZSM-5分子筛后，接着引入锆制备的磷锆复合改性分子筛水热老化试样PLZ-Z 5 L保留有最多的微孔结构和总酸量；当含PLZ-Z 5试样组分制备的催化助剂应用于重油催化裂化反应时，具有最高的丙烯和液化气收率，分别为8.66%和28.41%。

Effect of preparation methods on phosphorus-zirconium composite modified ZSM-5 zeolites and their catalytic cracking properties

The preparation of phosphorus（P）-modified ZSM-5 zeolites by combined adopting different methods such as drying， calcinating and hydrothermal deactivation treatments were taken as the basis， subsequently， zirconium（Zr）was added to the previous modified zeolites to prepare series of P-Zr composite modified ZSM-5 zeolites samples （labeled as PHZ-Z 5， PBZ-Z 5， PLZ-Z 5）， and the catalytic cracking additives were also prepared with the composite modified zeolites as active components， and the P-Zr composite modified zeolites after hydrothermal deactivation treatment were characterized by XRD， BET， NH3-TPD， XPS， etc. The effects of the catalytic additives prepared by different modification methods on the production of propylene by catalytic cracking of heavy oil were evaluated on the advanced cracking evaluation unit（ACE）. The results showed that: after the P-modified ZSM-5 zeolites were prepared by the combination of drying， calcinating and hydrothermal deactivation treatments sequentially， the P-Zr composite modified zeolite sample PLZ-Z 5 L was prepared by introducing Zr， then add the P-Zr composite modified zeolite sample PLZ-Z 5 prepared by introducing Zr， and it could retain the most microporous structure and total acid amount after hydrothermal aging treatment. Moreover， when the catalytic additive prepared from the PLZ-Z 5 sample was applied to the catalytic cracking reaction of heavy oil， which had the highest propylene and LPG（liquefied petroleum gas） yields of 8.66% and 28.41%， respectively.