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超声强化 MoO3/Al2O3 催化剂氧化脱除模型柴油中硫的工艺条件及强化效果研究。

Investigation of process variables and intensification effects of ultrasound applied in oxidative desulfurization of model diesel over MoO3/Al2O3 catalyst.

出版信息

Ultrason Sonochem. 2014 Mar;21(2):692-705. doi: 10.1016/j.ultsonch.2013.10.004.

Abstract

A new heterogeneous sonocatalytic system consisting of a MoO3/Al2O3 catalyst and H2O2 combined with ultrasonication was studied to improve and accelerate the oxidation of model sulfur compounds of diesel, resulting in a significant enhancement in the process efficiency. The influence of ultrasound on properties, activity and stability of the catalyst was studied in detail by means of GC-FID, PSD, SEM and BET techniques. Above 98% conversion of DBT in model diesel containing 1000 μg/g sulfur was obtained by new ultrasound-assisted desulfurization at H2O2/sulfur molar ratio of 3, temperature of 318 K and catalyst dosage of 30 g/L after 30 min reaction, contrary to the 55% conversion obtained during the silent process. This improvement was considerably affected by operation parameters and catalyst properties. The effects of main process variables were investigated using response surface methodology in silent process compared to ultrasonication. Ultrasound provided a good dispersion of catalyst and oxidant by breakage of hydrogen bonding and deagglomeration of them in the oil phase. Deposition of impurities on the catalyst surface caused a quick deactivation in silent experiments resulting only 5% of DBT oxidation after 6 cycles of silent reaction by recycled catalyst. Above 95% of DBT was oxidized after 6 ultrasound-assisted cycles showing a great improvement in stability by cleaning the surface during ultrasonication. A considerable particle size reduction was also observed after 3 h sonication that could provide more dispersion of catalyst in model fuel.

摘要

一种由 MoO3/Al2O3 催化剂和 H2O2 组成的新型多相声催化体系,结合超声处理,被研究用于改善和加速柴油模型硫化合物的氧化,从而显著提高了过程效率。通过 GC-FID、PSD、SEM 和 BET 技术详细研究了超声对催化剂性能、活性和稳定性的影响。在 H2O2/硫摩尔比为 3、温度为 318 K 和催化剂用量为 30 g/L 的条件下,经过 30 min 的反应,在含有 1000 μg/g 硫的模型柴油中,新的超声辅助脱硫可使 DBT 的转化率达到 98%以上,而在无声条件下,转化率仅为 55%。这种改进受到操作参数和催化剂性能的显著影响。与超声处理相比,在无声过程中使用响应面法研究了主要工艺变量的影响。超声通过打破氢键和使它们在油相中解团聚,为催化剂和氧化剂提供了良好的分散性。杂质在催化剂表面的沉积导致在无声实验中迅速失活,在用过的催化剂进行 6 次无声反应后,仅氧化了 5%的 DBT。在 6 次超声辅助循环后,氧化了 95%以上的 DBT,通过超声清洗表面,稳定性得到了很大提高。经过 3 h 的超声处理,还观察到颗粒尺寸显著减小,这可以在模型燃料中提供更多的催化剂分散。

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