石油炼制与化工 ›› 2020, Vol. 51 ›› Issue (8): 37-42.

• 催化剂 • 上一篇    下一篇

介孔H-ZSM-5分子筛的制备及以其为载体的催化剂的催化裂化汽油加氢性能

李景锋,高海波,姚文君,向永生,张永泽,王高峰,瞿朝霞,边虎   

  1.  中国石油石油化工研究院兰州化工研究中心
  • 收稿日期:2020-03-16 修回日期:2020-04-13 出版日期:2020-08-12 发布日期:2020-08-27
  • 通讯作者: 向永生 E-mail:xiangyongsheng@petrochina.com.cn
  • 基金资助:
     

PREPARATION OF MESOPOROUS ZSM-5 ZEOLITE AND ITS PERFORMANCE IN FCC GASOLINE HYDROFINING

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  • Received:2020-03-16 Revised:2020-04-13 Online:2020-08-12 Published:2020-08-27
  • Contact: Xiang Yongsheng E-mail:xiangyongsheng@petrochina.com.cn
  • Supported by:
     

摘要: 以廉价的橡胶乳液-3为介孔模板剂,通过优化晶化温度、晶化时间和凝胶中橡胶乳液-3干基与硅元素的质量比(R),以及采用蒸汽/柠檬酸组合处理,获得孔结构和酸性适宜的介孔H-ZSM-5分子筛,并对以此分子筛为载体制备的辛烷值恢复催化剂进行催化裂化汽油(催化汽油)加氢性能评价。表征结果表明:R、晶化温度和晶化时间的最佳值依次为0.26,190 ℃,48 h;蒸汽/柠檬酸组合处理在显著提高介孔H-ZSM-5分子筛介孔比例的同时可在较大范围内调控其酸性。以硫质量分数为113 μg/g、烯烃体积分数为40.9%的催化汽油为原料的加氢性能评价结果表明:与上一代工业化辛烷值恢复催化剂相比,新制备的辛烷值恢复催化剂作用下的加氢产品的烯烃体积分数降低2.2百分点,异构烷烃体积分数增加1.1百分点,芳烃体积分数增加1.1百分点,脱硫率增加11.5百分点,研究法辛烷值(RON)损失减小0.5个单位,液体收率相当。介孔H-ZSM-5分子筛具有较大平均孔径、较高强L酸酸量与B酸酸量的比值、较多弱酸量,有利于提高其对催化汽油降烯烃、保持高RON和高液体收率的能力;其较大平均孔径有利于活性金属在介孔分子筛中的分散,从而使其对催化汽油表现出较高的脱硫性能。

关键词: 介孔ZSM-5分子筛, 制备, 催化汽油, 加氢精制, 酸性

Abstract: The mesoporous H-ZSM-5 zeolite with moderate pore structure and acidity was prepared by optimization of crystallization time, crystallization temperature and mass ratio of rubber latex-3/silicon in gel(R) using cheap rubber latex-3 as the mesoporous template,followed by steaming/citric acid combination treatments. The hydrogenation performance of FCC gasoline was evaluated for the octane number recovery catalyst prepared on the basis of this molecular sieve. The characterization results indicated that the optimum value of crystallization time, crystallization temperature and R was 48 h, 190 ℃ and 0.26, respectively. In addition, the combination treatments not only markedly increased the mesoporous ratio of H-ZSM-5 zeolite but also regulated its acidity in a wide range. The FCC gasoline with a sulfur content of 113 μg/g and a olefin volume fraction of 40.9% was used for the evaluation of the octane recovery catalyst. The hydrotreated gasoline by newly prepared catalyst, compared with that of industrial catalyst, had lower volume fraction of alkenes by 2.2 percentage points, higher volume fraction of iso-alkanes by 1.1 percentage points, higher volume fraction of aromatics by 1.1 percentage points,whilet he desulfurization rate increased by 11.5 percentage points, and the loss in research octane number (RON) decreased by 0.5 unit with the same liquid yield. The results indicated that the bigger average pore, higher ratio of strong Lewis acidity/Bronsted acidity and more weak acidity contribute to decrease olefin and sulfur content, to hold RON and to increase liquid yield of hydrotreated FCC gasoline product. Moreover, the bigger average pore is beneficial to the dispersion of active metals in mesoporous molecular sieves, so as to make it show higher desulfurization performance for FCC gasoline.

Key words: mesoporous ZSM-5, preparation, FCC gasoline, hydrofining, acidity

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