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Heavy oil hydroprocessing over supported NiMo sulfided catalyst: An inhibition effect by added H_2S

机译:负载型NiMo硫化催化剂上的重油加氢处理:添加H_2S的抑制作用

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摘要

The influence of H_2S (0-559.6 kPa) on Maya crude hydrotreating is investigated in an integral fixed bed up-flow micro reactor. The added H_2S inhibits hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) while asphaltene conversion (HDAs) remained almost unaffected. On the other hand, a promotional effect is found for hydrodemetallization (HDM). The observed variation in HDS and HDM conversions suggests a dual nature of catalytic sites particularly at high partial pressure of hydrogen sulfide. The promotional effect for HDM may be interpreted in terms of adsorption of metal-porphyrins on Broensted acid sites (sulfhydryl group), which enhance hydrogenation of metal-porphyrins and convert them into the corresponding metal-chlorin structure in a first step of reaction. The final step in the HDM is essentially hydrogenolysis (metal-nitrogen) and requires the presence of an anionic vacancy (CUS). The conversion of asphaltene is also depending on the acidic nature of sulfided catalyst that is remaining either uninhibited or slightly enhanced with H_2S.
机译:在整体固定床上流微反应器中研究了H_2S(0-559.6 kPa)对Maya粗加氢处理的影响。加入的H_2S抑制加氢脱硫(HDS)和加氢脱氮(HDN),而沥青烯转化率(HDA)几乎不受影响。另一方面,发现了加氢脱金属(HDM)的促进作用。 HDS和HDM转化率的观察到的变化表明催化位点具有双重性质,尤其是在硫化氢的高分压下。 HDM的促进作用可以用金属卟啉在Broensted酸位点(巯基)上的吸附来解释,它增强了金属卟啉的氢化作用,并在第一步反应中将其转化为相应的金属-二氢卟酚结构。 HDM的最后一步基本上是氢解(金属氮),并且需要存在阴离子空位(CUS)。沥青质的转化率还取决于硫化的催化剂的酸性,该酸性不受抑制或被H_2S增强。

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