Catalytic oxidative desulfurization of model and real diesel over a molybdenum anchored metal-organic framework
Catalytic oxidative desulfurization of model and real diesel over a molybdenum anchored metal-organic framework
复制标题
模型柴油和真实柴油在钼锚定金属有机骨架上的催化氧化脱硫
DOI：
10.1016/j.micromeso.2018.11.004
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发表时间：
2019
影响因子：
5.2
通讯作者：
Van der Voort Pascal
中科院分区：
文献类型：
--
作者：
Liu Ying Ya;Leus Karen;Sun Zhichao;Li Xiang;Depauw Hannes;Wang Anjie;Zhang Jian;Van der Voort Pascal
在本工作中，我们报告了MoO 2Cl 2锚定的金属-有机框架，Mo@COMOC-4，在氧化脱硫（ODS）过程中的催化性能在连续固定床反应器。考察了Mo@COMOC-4作为催化剂在含二苯并噻吩（DBT）、苯并噻吩（BT）和4，6-二甲基二苯并噻吩（4，6-DMDBT）的模型油中的氧化作用。以叔丁基过氧化氢（TBHP）为氧化剂，在70 °C下进行50 h的ODS反应，DBT的转化率沿着升高，达80%以上，氧化剂利用率达85%以上，DBT迅速转化为DBT砜。XRD和ICP分析表明，Mo@COMOC-4的结构得到了很好的保留，没有明显的Mo物质浸出。此外，Mo@COMOC-4对加氢柴油也有氧化作用，其脱硫效率为74%，乙腈萃取后的萃取回收率为92.5%。光谱表征证实了TBHP处理下MoO 2Cl 2生成了钼过氧化物络合物，并根据实验证据以及FT-IR和FT-FIR表征结果提出了合理的催化过程。
In this work, we report the catalytic performance of a MoO2Cl2anchored metal-organic framework, Mo@COMOC-4, in the oxidative desulfurization (ODS) process on a continuous fixed-bed reactor. Mo@COMOC-4 was examined as a catalyst in the oxidation of model oils containing dibenzothiophene (DBT), benzothiophene (BT) or 4,6-dimethyldibenzothiophene (4,6-DMDBT). In a 50-h ODS reaction of DBT at 70 °C, withtert-butyl hydroperoxide (TBHP) as the oxidant, a constant high DBT conversion of nearly 80% was observed along with a high oxidant utility of over 85%, where DBT was converted rapidly into DBT sulfone. XRD and ICP analysis show that the structure of Mo@COMOC-4 was well preserved, with no significant leaching of Mo species. In addition, Mo@COMOC-4 can also oxidize a hydrogenated diesel oil, and 74% sulfur removal efficiency was achieved, with an extraction recovery of 92.5% after acetonitrile extraction. Spectroscopic characterization confirmed the formation of a molybdenum peroxide complex from MoO2Cl2under TBHP treatment, a plausible catalytic process was proposed based on the experiment evidence as well as FT-IR and FT-FIR characterization results.