高硅铝比小晶粒NaY分子筛/高岭土复合物的合成及其催化裂化性能

摘要/Abstract

摘要： 以两种不同粒径的高岭土为原料,采用水热法合成了高硅铝比小晶粒NaY分子筛/高岭土复合物,通过XRD、SEM、晶粒度分析和N₂物理吸附等表征手段对复合物进行了结构和形貌表征。结果表明,与商品NaY相比,高岭土合成样品的结构稳定性和水热稳定性显著提高,以细化高岭土为原料合成样品的晶粒尺寸达310 nm,比表面积达807 m²·g^-1。以改性NaY分子筛/高岭土复合物为活性组分制备了催化裂化催化剂,采用NH₃程序升温脱附(NH₃-TPD)技术对其酸性特征进行了分析,并在小型微反装置上对其重油催化裂化性能进行了评价。研究结果发现,随着骨架硅铝比增大,催化剂表面酸中心强度增加,而酸量下降。采用细化高岭土合成的NaY分子筛/高岭土复合物的分子筛晶粒更小,催化剂酸中心数量以及催化裂化性能均大幅度提升。随着高温焙烧高岭土/偏高岭土质量比的增加,合成产物中的高岭土基质含量增加,催化剂表面酸中心强度下降。以原料高温焙烧高岭土/偏高岭土质量比为0.5,骨架硅铝比为6.1(摩尔比)的样品制备的催化剂,去柴重油转化率高达85.4%,同时有高达64.2%的汽油收率,表现出优异的重油催化裂化性能。

关键词: NaY分子筛, 高岭土, NaY分子筛/高岭土复合物, 水热法, 硅铝比, 晶粒尺寸, 催化裂化

Abstract: Small-sized NaY zeolite/kaolin composites with high framework SiO₂/Al₂O₃ ratio were hydrothermally synthesized from two kaolins with different particle sizes. The structure and morphology of composites were characterized by XRD, SEM, grain size analysis and N₂ physical adsorption techniques. The results show that compared with commercial NaY, the structure stability and hydrothermal stability of samples synthesized from kaolin are significantly improved. The grain size of the sample synthesized from fine kaolin is 310 nm, and the specific surface area is 807 m²·g^-1. The catalytic cracking catalysts were prepared by using modified NaY zeolite/kaolin composite as active component. The acidity of the catalysts was characterized by NH₃-TPD, and the heavy oil catalytic cracking performance was evaluated on microreactor. The results show that the acid center strength of sites on catalysts increases with the increase of framework SiO₂/Al₂O₃ ratio, while the acid center amount decreases. The grain size of NaY zeolite/kaolin composites synthesized from fine kaolin is smaller. The number of acid centers and catalytic cracking performance of catalysts prepared by small-sized NaY zeolite/kaolin composites are greatly improved. With the increase of m(calcined kaolin)/m(metakaolin), the content of substrate in NaY zeolite/kaolin composites increases, while the acid center strength of catalysts decreases. The catalyst prepared by the sample with framework SiO₂/Al₂O₃ molar ratio of 6.1 and m(calcined kaolin)/m(metakaolin) of 0.5 presents excellent catalytic cracking performance of heavy oil. And the conversion rate of heavy oil (diesel excluded) is as high as 85.4%, and the gasoline yield is up to 64.2%.

Key words: NaY zeolite, kaolin, NaY zeolite/kaolin composite, hydrothermal method, SiO₂/Al₂O₃ ratio, grain size, catalytic cracking

中图分类号:

TQ426.6

王文凯, 谭涓, 王诗涵, 邱鑫. 高硅铝比小晶粒NaY分子筛/高岭土复合物的合成及其催化裂化性能[J]. 硅酸盐通报, 2021, 40(10): 3479-3489.

WANG Wenkai, TAN Juan, WANG Shihan, QIU Xin. Synthesis and Catalytic Cracking Performance of Small-Sized NaY Zeolite/Kaolin Composites with High Framework SiO₂/Al₂O₃ Ratio[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(10): 3479-3489.

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