石油炼制与化工 ›› 2020, Vol. 51 ›› Issue (9): 71-78.

• 催化剂 • 上一篇    下一篇

磷、镍改性丝光分子筛催化剂上四氢萘加氢裂解反应性能

李经球1,2,3,丁键3,石张平3,孙承林1,孔德金3   

  1. 1. 中国科学院大连化学物理研究所
    2. 中国科学院大学
    3. 中国石化上海石油化工研究院绿色化工与工业催化国家重点实验室
  • 收稿日期:2020-02-03 修回日期:2020-05-24 出版日期:2020-09-12 发布日期:2020-09-27
  • 通讯作者: 李经球 E-mail:ljq198232@aliyun.com

HYDROCRACKING OF TETRALIN OVER PHOSPHOROUS AND NICKEL MODIFIED MORDENITE ZEOLITE CATALYSTS

  • Received:2020-02-03 Revised:2020-05-24 Online:2020-09-12 Published:2020-09-27

摘要: 以丝光分子筛为载体,采用浸渍法制备系列磷、镍改性的分子筛催化剂,并利用X射线衍射、吡啶吸附红外光谱、NH3-程序升温脱附、固体魔角自旋核磁共振和氮气吸附-脱附等手段对催化剂进行表征。结果表明:磷通过与分子筛骨架铝的相互作用减弱了酸强度,同时通过脱铝作用形成丰富的L酸中心;镍的引入能与骨架铝作用形成扭曲四配位铝结构,但并不显著影响分子筛的酸性质。在四氢萘的加氢裂解反应过程中,助剂镍通过氢迁移与酸性位形成协同催化作用并极大地提高了分子筛的加氢裂解活性,而磷改性分子筛则具有更优良的抗积炭能力及催化稳定性。通过磷-镍复合改性的催化剂具有适当的加氢功能及优化的酸性分布,可提高四氢萘转化率及单环芳烃产物选择性,同时改善催化剂的运行稳定性。

关键词: 四氢萘, 加氢裂解, 磷, 镍, 丝光分子筛

Abstract: A series of P, Ni modified mordenite zeolite catalysts were prepared via impregnation, and systematically characterized by using XRD, FT-IR, NH3-TPD, 27Al NMR, 31P NMR, and nitrogen adsorption-desorption techniques. The results demonstrated that P efficiently weakened the acid strength through the coordination with the framework aluminum of zeolites, and simultaneously formed abundant L acid center through dealumination. Meanwhile, the introduction of Ni interacted with framework aluminum to form twisted tetra coordinated aluminum structure, but does not affect significantly the acid properties of zeolites. In the hydrocracking process of tetralin over those modified zeolites, Ni promoter greatly improved the hydrocracking activity of tetralin through H spillover between metal and acid site, while P modified zeolites exhibited better anti-coking ability and catalyst stability. The catalyst modified by the combination of phosphorus and nickel has appropriate hydrogenation function and optimized acid distribution, which improves the conversion rate of tetralin and the selectivity of single cyclic aromatic hydrocarbon, and also improves the operational stability of the catalyst.

Key words: tetralin, hydrocracking, phosphorus, nickel, mordenite sieve