Preparation of C9H10O2-0.5ZnCl2/Al2O3 and its oxidative desulfurization performance
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摘要: 通过将C9H10O2-0.5ZnCl2双酸型低共熔溶剂固载到Al2O3上制备了C9H10O2-0.5ZnCl2/Al2O3催化剂。该催化剂采用XRD、FT-IR、SEM、EDS、N2吸附-脱附技术进行了分析。以C9H10O2-0.5ZnCl2/Al2O3为催化剂,过氧化氢为氧化剂研究模拟油中芳香族硫化物的脱除性能。考察反应参数如温度、催化剂加入量、O/S物质的量比、硫化物类型等对催化剂脱硫活性的影响。实验结果表明,在模拟油为5 mL、催化剂量为0.2 g、O/S比为8、反应温度为60 ℃、反应时间为180 min的条件下,模拟油中二苯并噻吩(DBT)脱硫率为99.2%。此外,在模拟油氧化脱硫中催化剂循环使用六次,其氧化脱硫活性略有降低。研究了C9H10O2-0.5ZnCl2/Al2O3催化氧化脱硫的反应机理。Abstract: A C9H10O2-0.5ZnCl2/Al2O3 catalyst was successfully prepared by immobilizing phenylpropionic acid-zinc chloride(C9H10O2-0.5ZnCl2) double acid deep eutectic solvent on Al2O3, and analyzed by XRD, FT-IR, SEM, EDS and N2 adsorption-desorption. The removal activity for aromatic sulfides in model oil using C9H10O2-0.5ZnCl2/Al2O3 as catalysis and H2O2 as oxidant and the effect of some reaction parameters such as temperature, catalyst dosage, O/S molar ratio and different sulfide types on the desulfurization activity of catalyst were investigated. The experimental results show that with the model oil of 5 mL, the catalyst dosage of 0.2 g and the O/S molar ratio of 8, at temperature of 60℃and reaction time of 180 min, the removal rate of DBT can reach to 99.2%. In addition, the catalyst can be recycled up to 6 times with a little decrease in catalytic activity for the ODS process. The catalysis-oxidation desulfurization mechanism of C9H10O2-0.5ZnCl2/Al2O3 was also explored.
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Key words:
- zinc chloride /
- alumina /
- oxidation desulfurization /
- deep eutectic solvents
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表 1 样品的表面结构表征
Table 1 Surface structural characteristics of samples
Sample Surface A/(m2·g-1) Pore volume v/(cm3·g-1) Pore size d/nm Al2O3 346.5 1.164 0.5086 C9H10O2-0.5ZnCl2/Al2O3 171.4 0.5684 0.9976 表 2 不同脱硫体系脱硫活性对比
Table 2 Comparison of desulfurization performance of different desulfurization systems
Desulfurization systems Removal rate of DBT η/% H2O2/Al2O3[a] 20 H2O2/C9H10O2-0.5ZnCl2[b] 38 H2O2/C9H10O2-0.5ZnCl2/Al2O3[c] 99.2 reaction condition: a: 5 mL model oil, 60 ℃, O/S= 8, 0.133 g Al2O3, t=180 min; b: 5 mL model oil, 60 ℃, O/S= 8, 0.067 g C9H10O2-0.5ZnCl2, t=180 min; c: 5 mL model oil, 60 ℃, O/S= 8, 0.2 g C9H10O2-0.5ZnCl2/Al2O3, t=180 min 表 3 C9H10O2-0.5ZnCl2/Al2O3的重复使用性能
Table 3 Recycling performance of C9H10O2-0.5ZnCl2 /Al2O3
Recycle times 1 2 3 4 5 6 Sulfur removal η/% 99.2 96.2 95.4 92.3 88.3 85.1 -
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