化工学报 ›› 2021, Vol. 72 ›› Issue (11): 5653-5663.DOI: 10.11949/0438-1157.20210457

• 催化、动力学与反应器 • 上一篇    下一篇

ZrO2/SiO2催化剂的制备及其氧化脱硫性能研究

刘晓艺(),李秀萍,赵荣祥(),张豪   

  1. 辽宁石油化工大学石油化工学院,辽宁 抚顺 113001
  • 收稿日期:2021-04-06 修回日期:2021-09-27 出版日期:2021-11-05 发布日期:2021-11-12
  • 通讯作者: 赵荣祥
  • 作者简介:刘晓艺(1994—),女,硕士研究生,1550466549@qq.com
  • 基金资助:
    辽宁省自然科学基金指导计划项目(2019-ZD-0064)

Preparation of ZrO2/SiO2 catalyst and its oxidative desulfurization performance

Xiaoyi LIU(),Xiuping LI,Rongxiang ZHAO(),Hao ZHANG   

  1. School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China
  • Received:2021-04-06 Revised:2021-09-27 Online:2021-11-05 Published:2021-11-12
  • Contact: Rongxiang ZHAO

摘要:

以己内酰胺-八水氧氯化锆低共熔溶剂为添加组分,采用溶胶-凝胶法合成含锆的硅胶,再经过高温煅烧得到n-ZrO2/SiO2 n=2%,4%,6%) 负载型催化剂。并用红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)、N2吸附-脱附、X射线光电子能谱(XPS)对其进行结构表征,确定ZrO2成功负载到SiO2上。以ZrO2/SiO2为催化剂和吸附剂,H2O2为氧化剂组成催化氧化脱硫体系,并应用于模拟油脱硫。分别考察了氧化锆负载量、反应温度、氧硫比、催化剂加入量及不同类型的硫化物对脱硫效果的影响。实验结果表明,在反应温度为70℃、n(H2O2)/n(S)=4(摩尔比)、4%-ZrO2/SiO2的加入量为0.2 g的最佳反应条件下,氧化脱硫体系对二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)和苯并噻吩(BT)的脱除率分别为98.7%、93%和65.9%。且4%-ZrO2/SiO2回收利用5次后,DBT脱除率仍可达到91.8%。

关键词: ZrO2/SiO2, 二苯并噻吩, 溶胶, 氧化, 脱硫

Abstract:

With caprolactam-zirconium oxychloride octahydrate deep eutectic solvent as an additive component, a sol-gel method is used to synthesize zirconium-containing silica-gel, and then through a high-temperature calcination process to obtain n-ZrO2/SiO2 (n=2%, 4%, 6%) catalyst. The catalyst were characterized through Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results show that ZrO2 was successfully loaded onto SiO2. The desulfurization of a model oil was investigated using ZrO2/SiO2 as the catalyst and adsorbent, H2O2 as the oxidant. The effects of ZrO2 loading, reaction temperature, the molar ratio of O/S, catalyst dosage, and different types of sulfides on the desulfurization were investigated respectively. The experimental results show that under the optimal reaction conditions of 4%-ZrO2/SiO2, 70℃ reaction temperature, n(H2O2)/n(S)=4, 4%-ZrO2/SiO2 dosage of 0.2 g, the sulfur removal rates of DBT, 4,6-DMDBT and BT were 98.7%, 93% and 65.9%. After 4%-ZrO2/SiO2 was recycled for 5 times, the desulfurization rate of DBT reached 91.8%.

Key words: ZrO2/SiO2, dibenzothiophene, gels, oxidation, desulfurization

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