改性固体超强酸S2O82-/ZrO2-CoO用于FCC汽油氧化脱硫的研究

以硝酸锆、硝酸铜和硝酸钴为金属源，过硫酸铵作为浸渍液，采用共沉淀浸渍法合成出固体超强酸催化剂S₂O₈^2-/ZrO₂、S₂O₈^2-/ZrO₂-CuO和S₂O₈^2-/ZrO₂-CoO，通过XRD、FT-IR、NH₃-TPD、BET对催化剂进行表征。结果表明，Co（钴）改性催化剂S₂O₈^2-/ZrO₂-CoO在三种催化剂中超强酸位最多。将其作为催化剂，过氧化氢作为氧化剂用于FCC汽油氧化脱硫反应，研究不同反应温度、催化剂用量、反应时间、氧化剂用量对FCC汽油脱硫效果的影响。结果表明，FCC汽油氧化脱硫的最佳条件为：反应温度70 ℃，反应1.5 h，FCC汽油加入量与氧化剂体积比7.5：1，催化剂用量0.02 g/mL。反应产物利用N，N-二甲基甲酰胺进行萃取分离，萃取剂/汽油体积比为1：1时，FCC汽油脱硫率最高可达85.34%，回收率为94.45%，并且催化剂表现出较为稳定的催化活性。

Modified solid superacid S2O82-/ZrO2-CoO for oxidative desulfurization of FCC gasoline

A series of solid super acid catalysts, S₂O₈^2-/ZrO₂, S₂O₈^2-/ZrO₂-CuO and S₂O₈^2-/ZrO₂-CoO, were synthesized by coprecipitation impregnation method with zirconium nitrate, copper nitrate and cobalt nitrate as the metal sources and with ammonium persulfate as the impregnation solution. The catalysts were characterized by XRD, FT-IR and NH₃-TPD. The characterization shows that the S₂O₈^2-/ZrO₂-CoO catalyst has the most super acid sites among the three catalysts. S₂O₈^2-/ZrO₂-CoO as the catalyst and hydrogen peroxide as the oxidant were used for oxidative desulfurization of FCC gasoline, and the effects of reaction temperature, catalyst dosage, reaction time and oxidant dosage on the desulfurization of FCC gasoline were studied. The optimal conditions were determined as:FCC gasoline of 15 mL, reaction temperature of 70℃, reaction time of 1.5 h, oxidant dosage of V(H₂O₂):V(oil)=7.5:1, and catalyst dosage of 0.02 g/mL. Moreover, the reaction product was extracted with N,N-dimethylformamide. When the volume ratio of extractant to gasoline is 1:1, the sulfur removal efficiency and recovery of FCC gasoline reach to 85.34% and 94.45%, respectively. The catalyst exhibits a relatively stable catalytic activity.