Modified solid superacid S2O82-/ZrO2-CoO for oxidative desulfurization of FCC gasoline
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摘要: 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S2O82-/ZrO2、S2O82-/ZrO2-CuO和S2O82-/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S2O82-/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。Abstract: A series of solid super acid catalysts, S2O82-/ZrO2, S2O82-/ZrO2-CuO and S2O82-/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 S2O82-/ZrO2-CoO catalyst has the most super acid sites among the three catalysts. S2O82-/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.
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Key words:
- solid super acid /
- oxidative desulfurization /
- impregnation method /
- FCC gasoline
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表 1 不同催化剂的BET数据
Table 1 BET data of different catalysts
Catalyst Surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore diameter d/nm S2O82-/ZrO2 102.2 0.129 1.83 S2O82-/ZrO2-CuO 114.1 0.098 0.96 S2O82-/ZrO2-CoO 130.9 0.071 0.55 表 2 直接萃取与反应后再萃取对脱硫率的影响
Table 2 Effect of direct extraction and extraction after reaction on the desulfurization efficiency
Extraction Desulfurization efficiency η/% Recovery /% Direct extraction 49.85 95.33 Extraction after reaction 85.34 94.45 表 3 FCC汽油氧化脱硫反应前后的硫形态分布
Table 3 Distribution of sulfur form before and after oxidative desulfurization of FCC gasoline
Apex RT Species of sulfide Distribution w/% sbefore safter 1.27 hydrothion 35.32 - 1.33 methanthiol 36.19 8.92 1.47 ethanethiol 136.83 33.93 1.65 isopropyl mercaptan 32.89 8.14 1.94 n-propyl mercaptan 50.37 12.60 2.48 thiophene 166.31 41.30 3.14 n-butyl mercaptan 10.83 2.71 4.62 2-methylthiophene 94.12 23.46 4.84 3-methylthiophene 125.76 - 5.69 tetrahydrothiophene 57.05 - 6.93 C6-thioether 15.12 3.68 7.51 2-methyltetrahydrothiophene 15.89 - 8.69 2-ethylthiophene 61.67 - 9.35 2、4-dimethylthiophene 77.92 19.2 9.83 2、3-dimethylthiophene 55.92 - 10.64 3、5-dimethylthiophene 31.86 - 15.23 C3-thiophene 34.18 - 15.4 C3-thiophene 12.50 - 15.86 C3-thiophene 36.53 9.11 17.05 C3-thiophene 8.47 - 17.84 C3-thiophene 31.61 - 21.88 C4-thiophene 19.31 4.85 23.65 C4-thiophene 6.54 - 24.51 C4-thiophene 6.76 - 25.38 C4-thiophene 9.22 - 30.06 benzothiophene 76.84 19.00 34.26 C4-thiophene 6.80 - 36.38 methylbenzothiophene 11.6 - 36.95 methylbenzothiophene 11.05 - 37.44 methylbenzothiophene 8.17 - 37.8 methylbenzothiophene 12.32 3.10 Total 1295.96 190.02 -
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