ZrO_(2)/SiO_(2)催化剂的制备及其氧化脱硫性能研究

Preparation of ZrO_(2)/SiO_(2) catalyst and its oxidative desulfurization performance

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-ZrO_(2)/SiO_(2)(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ZrO_(2)成功负载到SiO_(2)上。以ZrO_(2)/SiO_(2)为催化剂和吸附剂,H_(2)O_(2)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(H_(2)O_(2))/n(S)=4(摩尔比)、4%-ZrO_(2)/SiO_(2)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%-ZrO_(2)/SiO_(2)回收利用5次后,DBT脱除率仍可达到91.8%。

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-ZrO_(2)/SiO_(2)(n=2%,4%,6%)catalyst.The catalyst were characterized through Infrared spectroscopy(FT-IR),X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 adsorptiondesorption,and X-ray photoelectron spectroscopy(XPS).The characterization results show that ZrO_(2) was successfully loaded onto SiO_(2).The desulfurization of a model oil was investigated using ZrO_(2)/SiO_(2) as the catalyst and adsorbent,H_(2)O_(2) as the oxidant.The effects of ZrO_(2) 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%-ZrO_(2)/SiO_(2),70℃reaction temperature,n(H_(2)O_(2))/n(S)=4,4%-ZrO_(2)/SiO_(2) 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%-ZrO_(2)/SiO_(2) was recycled for 5 times,the desulfurization rate of DBT reached 91.8%.