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Development of hydrodesulfurization catalyst using comparative model feed reactions and quantum chemical studies.

机译:利用比较模型饲料反应和量子化学研究的加氢脱硫催化剂的研制。

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Model hydrodesulfurization (HDS) catalysts (Ni2.75W21, Co2.75Moll, Ni2.75Moll and Ni0.9Co1.85Moll wt% / γ-Al2O3) were used in the HDS of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), with and without addition of H2S or NH3. The NiCoMo catalyst exhibited the highest HDS performance with the additives, while NiMo was the best catalyst without the additives. A comparison of the HDS reaction mechanism via hydrogenation (HYD) and the direct desulfurization (DDS) rate constants among these catalysts showed that the ranking of HYD and DDS rate constants depended on the catalyst and the additives. The behavior of NiW was very similar to NiMo. The total rate constants (HYD + DDS) of NiCoMo were the sums of higher HYD and DDS between the NiMo and CoMo. These results showed that the NiCoMo had two kinds of active sites, similar to NiMo and CoMo. Quantum chemical studies were applied to study the inhibitions of the additives on NiW, CoMo and NiMo metal edge surfaces. The active site structure of NiW was similar to that of NiMo. The ranking of the adsorption energies of the additives on each surface was in good agreement with experiments. The ideas derived from these model feed reactions in combination with quantum chemical studies contributed to the development of novel improved catalysts which played an integral part in our new HDS process.
机译:模型的加氢脱硫(HDS)催化剂(Ni2.75W21,Co2.75Moll,Ni2.75Moll和Ni0.9Co1.85Moll重量%/γ-Al2O3催化剂)在二苯并噻吩的加氢脱硫(DBT)和4,6-二甲基(4被使用, 6-DMDBT),添加和不添加H 2 S或NH 3的。该NiCoMo催化剂表现出与添加剂最高的HDS性能,同时的NiMo是没有添加剂的最佳催化剂。通过这些催化剂中加氢(HYD)和直接脱硫(DDS)速率常数的HDS反应机理的比较表明,排名HYD和DDS速率常数取决于催化剂和添加剂。的NiW的行为是非常相似的NiMo。总速率常数NiCoMo的(HYD + DDS)较高HYD的的NiMo和的CoMo之间的总和和DDS。这些结果表明,NiCoMo有复合有效部位,类似的NiMo和科莫。量子化学研究被用于研究上的NiW,和的CoMo金属的NiMo边缘表面添加剂的压抑。 NiW体系的活性位点的结构是相似的NiMo的。每个表面上的添加剂的吸附能的排名是与实验吻合。从促成了新的改进催化剂的开发从而起到了我们新的HDS过程中不可或缺的一部分量子化学研究结合这些模型饲料反应得到的想法。

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