Aerobic ultra-deep desulfurization of diesel oil triggered by porous carbon supported organic molecular N-hydroxyphthalimide catalyst
Aerobic ultra-deep desulfurization of diesel oil triggered by porous carbon supported organic molecular N-hydroxyphthalimide catalyst
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DOI：
10.1016/j.colsurfa.2022.128455
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发表时间：
2022-01
期刊：
影响因子：
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通讯作者：
Xiang Gao;Wei Jiang;Xin An;Kun Zhu;Linhua Zhu;Peiwen Wu;Wenshuai Zhu;Hua-ming Li
中科院分区：
文献类型：
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作者：
Xiang Gao;Wei Jiang;Xin An;Kun Zhu;Linhua Zhu;Peiwen Wu;Wenshuai Zhu;Hua-ming Li
分子氧以其廉价易得、环境友好等优点成为各种反应中理想的氧化剂。然而，在大气条件下，在短的反应时间内，它很难被活化。采用浸渍法将有机分子催化剂N-羟基邻苯二甲酰亚胺（NHPI）负载到石油焦基多孔炭（PC）表面。以乙酸钴为助催化剂，制备的NHPI/PC催化剂用于模拟柴油的好氧氧化脱硫，具有高效、可循环利用的特点。在最佳反应条件下，模型油中二苯并噻吩的转化率仅需3 h即可达到100.0%。此外，位阻较大的4-甲基二苯并噻吩和4，6-二甲基二苯并噻吩在4 h内仍能达到99. 2%和97. 2%。由于催化剂对氧化产物的吸附很大，硫含量可以降低到7 mg kg-1。在自由基捕获实验中，采用电子自旋共振检测超氧自由基。加入对苯醌后，DBT的转化率从100.0%下降到3.0%，进一步证实了超氧自由基是反应的主要活性物种。重复使用试验证明，该催化剂经过9次循环后仍具有较强的催化活性，具有良好的工业化前景。实际柴油中硫含量可从852 mg kg− 1降至91 mg kg−1，进一步表明该催化剂具有良好的工业应用前景。
Molecular oxygen is an ideal oxidant in various reaction because it is cheap, easily available, and environmentally friendly. However, it is hard to be activated under atmosphere condition within a short reaction time. In this study, the organic molecular catalyst N-hydroxyphthalimide (NHPI) was loaded on the surface of petroleum coke-based porous carbon (PC) via impregnation. Using cobalt acetate as a co-catalyst, the resulting NHPI/PC are demonstrated to be highly efficient and recyclable catalysts for aerobic oxidative desulfurization of model diesel oil. Under the optimal reaction conditions, the conversion rate of dibenzothiophene in the model oil could reach 100.0% in only 3 h. In addition, 4-methyldibenzothiophene and 4, 6-dimethyldibenzothiophene with greater steric hindrance can still reach 99.2% and 97.2% within 4 h. Due to the great adsorption of the catalyst to oxidative product, the sulfur content could decrease to 7 mg kg−1. In the free radical trapping experiment, superoxide radicals were detected by electron spin resonance. After adding p-benzoquinone, the conversion rate of DBT decreased from 100.0% to 3.0%, which further verified that superoxide free radical was the main active species. Reusability tests proved that the catalyst still had strong catalytic activity even after 9 cycles and might possess a good prospect of industrialization. In addition, the sulfur content in actual diesel oil could be decreased from 852 mg kg−1to 91 mg kg−1, which further indicated that the catalyst had a good prospect of industrial application.