Autocatalysis from the by-product metal sulfides plays a critical role in the residual oil hydrotreating (RHT) process. However, it has not been considered to build the catalyst deactivation models, which probably is one important reason that the widely used S-type deactivation models are inaccurate in predicting some RHT processes' deactivation profiles. A three-stage catalyst deactivation model was first developed to fill this gap based on the mechanism inferred from the experimental and literature data. This model accounts for active site formation from by-product metal sulfides, deactivation due to active site coverage by coke formation and metal deposition, active site poisoning by highly-adsorbed species, active phase sintering, and diffusion resistance from the pore blockage at the same time, resulting in a function of dimensionless metals-on-catalyst. Then, the effectiveness of the proposed model was evaluated using the industrial data of an RHT unit and the experimental data from the literature, either in combination with reaction kinetics or independently. Results showed that RHT processes with clear autocatalytic effects may display different types of deactivation profiles from the traditional "S" shape. However, the proposed model was able to accurately track the entire deactivation curve of the RHT process and well predict the product properties. This approach yields valuable insights into the intricate autocatalytic effect that remarkably contributes to the performance modification of RHT catalysts. It is highly recommended that further research should be conducted on this topic, as it shows great potential to significantly advance catalyst and process development.

A comprehensive insight into the evolution and molecular structure of basic and neutral nitrogen compounds during the residue hydrotreating(RHT) process was gained through ESI(+)/ESI(-) FT-ICR MS analysis of the feedstock and its hydrogenated samples, with hydrodenitrogenation(HDN) ratios of 15.9%-70.1%. This study revealed that carbazoles, characterized by a double bond equivalent(DBE) of 9-11,were the refractory neutral nitrogen compounds during the RHT process. Their recalcitrant nature was primarily due to their low aromaticity and high steric hindrance. Conversely, quinolines(DBEs 7 to 9)were the most abundant basic nitrogen compounds. Through a meticulous analysis of DBE evolution, we revealed the intricate reaction mechanisms of benzocarbazoles and dibenzocarbazoles in residual oil,highlighting the crucial role of quinolines as key intermediates in eliminating these compounds. Interestingly, nitrogen compounds with either low or high carbon numbers(for a given DBE) exhibited higher reactivity than those with medium carbon numbers, which can be attributed to the low steric hindrance resulting from short alkyl chains and more naphthenic-aromatic structures, respectively. After hydrotreatment, the molecular structures of the most refractory or abundant nitrogen compounds could consist of two main types: those with multiple naphthenic-aromatic rings and those with long side chains near the nitrogen atom. This research has revealed nitrogen compounds' evolutionary mechanisms and refractory nature, and the molecular structure of the most resistant or abundant basic and neutral nitrogen compounds, providing a deeper understanding of the HDN process and ultimately paving the way for the rational RHT catalyst design and process development.

在固定床渣油加氢试验装置上研究了催化裂化柴油(催化柴油)、煤油和催化裂化油浆在线清洗对渣油加氢催化剂活性和反应器压降的影响.首先采用催化柴油对运转中期的渣油加氢试验装置进行 72h在线清洗,结果表明,清洗后再通入渣油时加氢渣油的密度、残炭、硫含量和金属含量都显著降低,金属含量可长时间保持在较低水平.通过大幅提高反应温度模拟后部反应器压降升高现象,再分别采用煤油和催化裂化油浆对装置进行在线清洗,结果表明,使用煤油清洗后再通入渣油时反应器压降会很快再次升高,而使用催化裂化油浆清洗后再通入渣油运行 500 h后反应器压降未见上升,说明催化剂结焦导致反应器压降上升的问题可采用高芳香性催化裂化油浆间歇清洗的方式解决.

A deep insight into the molecular structure of the refractory sulfur compounds during residue hydrotreating process was realized by controlling the hydrodesulfurization (HDS) rate from 91.7% to 99.2%. The reactivity and the molecular-level evolution of the sulfur compounds were characterized by APPI FT-ICR MS and CID FT-ICR MS combined with HDS kinetic analysis. It was found that during deep RHT process, the increased reactivity order of sulfur families is mainly determined by the increased order of aromaticity and the decreased order of alkyl-substituted carbon number. Furthermore, the most refractory sulfur compounds have dominate double bond equivalent (DBE) of 10–12, followed by 9, and carbon number range of 36–38, and their skeleton typically include 2–3 aromatic rings and 0–1 naphthenic/cyclohexene ring, whose substitution positions near the sulfur atom may possibly be occupied by alkyl side chains with carbon number 4–9. This work reveals the reactivity order of individual sulfur compounds and its key influencing factors, and especially the molecular structure of the most refractory sulfur compounds, which may provide a deep understanding about the sulfur evolution.

某炼油厂双系列渣油加氢装置稳定运行3个周期,其加氢生成油性质好,是优质的催化裂化装置原料.运行过程中,三反温升下降速度快,影响装置操作,催化剂专利商通过催化剂级配调整,提高了三反温升并增强了其稳定性.为满足生产要求,装置在第4周期前进行扩能改造,更换了热高压分离器,彻底解决了热高分气带油的问题.

以5种不同的渣油为原料,从催化剂开发、催化剂级配、工艺条件优化、原料适应性考察等角度深入研究并开发了渣油深度加氢技术.结果表明:新开发的渣油深度加氢系列催化剂活性显著高于常规催化剂;反应温度是影响加氢深度最关键的因素;在优化的催化剂级配方案和工艺条件下,渣油深度加氢技术不仅可以显著提高原料中杂原子的脱除率,提高生成油的氢含量,还可以实现烃类定向转化多产化学品;高硫、低氮常压渣油更适宜采用渣油深度加氢技术生产优质催化裂解原料.

分别以石蜡基青海原油渣油(简称青海渣油)和中间基沙特阿拉伯轻质原油渣油(简称沙轻渣油)为原料,采用RHT系列渣油加氢催化剂进行了1500 h稳定性试验,采用傅里叶变换离子回旋共振质谱仪和核磁共振波谱仪分析原料和加氢生成油的分子结构差异及试验后催化剂(简称试验旧剂)上积炭组成.结果表明:青海渣油分子芳烃侧链多且长,通过初期快速升温可使其侧链断裂,改善其内扩散性能,且生焦倾向降低;沙轻渣油分子芳烃含量高,侧链较短,低温时即可达到较高杂质脱除率,高温则易生成结焦前身物,造成催化剂快速失活;与青海渣油相比,沙轻渣油加氢试验旧剂的积炭量更大,硬炭比例更高.对青海渣油加氢反应的温度分布进行优化,快速升高脱金属催化剂床层温度,降低脱硫剂反应温度,形成前高后低的温度分布,结果表明优化后方案的加氢生成油性质更优.