甲醇耦合抽余油芳构化反应催化剂制备及其催化性能研究

采用简单、快速、易工业化的一步法水热合成制备了ZSM-5/ZSM-11共晶分子筛，采用XRD、N₂吸附-脱附、NH₃-TPD、Py-IR、SEM和TEM等分析手段对ZSM-5/ZSM-11共晶分子筛进行了表征，并首次将成型催化剂应用于催化甲醇耦合抽余油芳构化反应体系中。结果表明：通过一系列表征手段证实了合成的分子筛为ZSM-5/ZSM-11共晶分子筛，具有多级孔结构，其比表面积为358 m²/g，孔体积0.35 cm³/g；具有B酸和L酸，B/L酸量比为2.07，晶体是由棒状的六方柱体插接而成的规则、棱角清晰的球体构成。在反应温度为380 ℃、反应压力为0.5 MPa、甲醇/抽余油质量比为1∶1、质量空速为1 h^-1的条件下，ZSM-5/ZSM-11共晶分子筛成型催化剂催化甲醇耦合抽余油芳构化反应时，C₅+收率大于81%，芳烃收率最高为38%。ZSM-5/ZSM-11共晶分子筛催化剂催化甲醇耦合抽余油芳构化反应具有良好的工业应用前景。

PREPARATION AND PERFORMANCE OF CATALYST FOR AROMATIZATION OF METHANOL COUPLING WITH RAFFINATE

Co-crystallized ZSM-5/ZSM-11 zeolite was prepared by one-step hydrothermal method, which was simple, rapid and easy to be industrialized. The samples were characterized by XRD, N₂ adsorption-desorption, Py-IR, SEM and TEM techniques. The results showed that the synthesized sample was ZSM-5/ZSM-11 co-crystallization zeolite with hierarchical pore structure, specific surface area of 358 m²/g, pore volume of 0.35 cm³/g, and B/L acid amount ratio of 2.07.And the crystalwas composed of regular, sharp-edged spheres with rod-shaped hexagonal cylinders. The formulated catalyst, by mixing the ZSM-5/ZSM-11 zeolites with alumina, was used in the aromatization reaction of methanol coupling with raffinate.Under the conditions of a reaction temperature of 380 °C, a reaction pressure of 0.5 MPa, a mass ratio of methanol to raffinate of 1:1 and a mass space velocity of 1 h^-1, the yield of C₅+ was over 81% withthe yield of aromatics up to 38%. Therefore, the ZSM-5/ZSM-11 co-crystallization zeolite has a good industrial application prospect in the catalytic aromatization of methanol coupling with raffinate.