化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2661-2672.DOI: 10.16085/j.issn.1000-6613.2023-2088

• 催化与材料技术 • 上一篇    

单晶多级孔ZSM-5分子筛酸性质对正庚烷催化裂解反应传质性能的影响

谢小金1(), 张晓雪1, 刘晓玲2, 崇明本2, 程党国1,2(), 陈丰秋1,2   

  1. 1.浙江大学化学工程与生物工程学院,浙江 杭州 310027
    2.浙江大学衢州研究院,浙江 衢州 324000
  • 收稿日期:2023-11-28 修回日期:2024-04-13 出版日期:2024-05-15 发布日期:2024-06-15
  • 通讯作者: 程党国
  • 作者简介:谢小金(1999—),男,硕士研究生,研究方向为催化反应工程。E-mail:xiexiaojin@zju.edu.cn
  • 基金资助:
    国家自然科学基金(22278353)

Effect of acidic properties of single-crystalline hierarchical ZSM-5 zeolite on its activity and mass transfer in n-heptane catalytic cracking

XIE Xiaojin1(), ZHANG Xiaoxue1, LIU Xiaoling2, CHONG Mingben2, CHENG Dangguo1,2(), CHEN Fengqiu1,2   

  1. 1.College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
    2.Institute of Zhejiang University-Quzhou, Quzhou 324000, Zhejiang, China
  • Received:2023-11-28 Revised:2024-04-13 Online:2024-05-15 Published:2024-06-15
  • Contact: CHENG Dangguo

摘要:

采用L-赖氨酸作为介孔模板剂,通过调控铝源(偏铝酸钠)添加量改变分子筛硅铝比,在单晶分子筛内部引入晶内介孔,成功地合成了一系列具有不同硅铝比的单晶多级孔ZSM-5分子筛,研究了其酸性质对正庚烷催化裂解反应传质性能的影响。利用X射线衍射(XRD)、N2物理吸附、氨气程序升温脱附(NH3-TPD)、吡啶红外(Py-IR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征了单晶多级孔ZSM-5分子筛的物理结构、酸性质和微观形貌。同时,利用零长柱(ZLC)装置测试获取了正庚烷在单晶多级孔ZSM-5分子筛中的表观扩散系数,用于反映其传质性能。研究结果表明,随着硅铝比的提高,单晶多级孔ZSM-5分子筛的物理结构基本保持一致;传质性能随酸量的减少而提升,催化裂解性能随酸量的增加而提高。当单晶多级孔ZSM-5分子筛的Si/Al从80提高至140,正庚烷的表观扩散系数提升了87%以上;当单晶多级孔ZSM-5分子筛的Si/Al=80时,正庚烷的转化率最高可达97.5%,乙烯和丙烯的选择性分别为24.3%和35.1%。

关键词: L-赖氨酸, 硅铝比, 单晶多级孔ZSM-5分子筛, 传质, 催化, 反应

Abstract:

Single-crystalline hierarchical ZSM-5 zeolite with intracrystalline mesopore was successfully synthesized by using L-lysine as a mesoporous template, and the Si/Al ratio was changed by adjusting the adding amount of aluminum source (sodium metaaluminate). Then the effect of acidic properties on zeolite’s activity and mass transfer in n-heptane catalytic cracking was investigated in detail. The physical structure, acidic properties and micromorphology of single-crystalline hierarchical ZSM-5 zeolite were characterized by using X-ray diffraction (XRD), nitrogen physical adsorption, ammonia temperature-programmed desorption (NH3-TPD), pyridine infrared (Py-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, the zero-length column (ZLC) device was employed to test the apparent diffusivity of n-heptane in single-crystalline hierarchical ZSM-5 zeolite,which was used to characterize its mass transfer performance. The results showed that the physical structure of single-crystalline hierarchical ZSM-5 zeolite kept almost the same with the increase of Si/Al ratio, while the zeolite’s mass transfer performance was improved with the decrease of acid amount, but the catalytic cracking performance was enhanced with the increase of acid amount. When the Si/Al ratio of the single-crystalline hierarchical ZSM-5 zeolite increased from 80 to 140, the apparent diffusivity of n-heptane could be improved by more than 87%. When the Si/Al ratio was 80, the conversion rate of n-heptane could reach up to 97.5%, and the selectivity of ethylene and propylene were 24.3% and 35.1%, respectively.

Key words: L-lysine, Si/Al ratio, single-crystalline hierarchical ZSM-5 zeolite, mass transfer, catalysis, reaction

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