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

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