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.

With the increasing demand for high-performance lithium-ion batteries (LIBs) in electric vehicles and portable electronic devices, rapid charging and long cycle life have become primary focuses in LIBs research. However, the poor rate performance of graphite anode materials and the suboptimal lithium-ion transport rate have constrained the development of LIBs. Herein, we synthesize a graphite anode material with a dual-layer coating structure of hard carbon (HC) and soft carbon (C) (G@HC@C) using a straightforward pre-oxidation and carbonization method. The hard carbon layer is formed by high-temperature carbonization of pre-oxidized pitch, characterized by an expanded interlayer spacing that facilitates rapid lithium-ion insertion and enhances capacity. The soft carbon outer layer helps to mitigate volume expansion during charge-discharge cycles and prevents direct contact between the graphite and the electrolyte, thereby enhancing electrode stability. The G@HC@C electrode exhibits excellent rate performance (119.5 mAh g-1 at 3 C) and maintains a cycle stability of 219.7 mAh g-1 after 1000 cycles at 1 C. This work offers new insights and methods for modifying graphite anode materials in fast-charging LIBs.

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.

高硫渣油深度加氢脱硫过程中,最难脱除的含硫化合物因有侧链取代、空间位阻效应强而最难转化,深度脱硫过程中,催化剂上金属(镍+钒)沉积及积炭均会加快.针对加氢脱金属剂及加氢脱硫降残炭剂分别开展级配比例的研究,结果表明:脱金属率随反应物流在脱金属催化剂上停留时间的增加而增加,脱硫率随反应物流在脱硫降残炭剂上停留时间的增加而增加,但在达到一定停留时间后的增加趋势均明显变缓;所开发的新型渣油加氢脱硫降残炭剂初始加氢脱硫活性不高,随着运行时间的延长活性有所提升并保持稳定.基于级配研究结果及加氢脱金属脱硫剂的特性,开发了新型高硫渣油深度加氢脱硫催化剂级配技术,并在高硫渣油固定床加氢装置上进行了工业应用.结果表明,新型级配催化剂具有良好的加氢脱硫活性及优异的稳定性,该固定床渣油加氢装置在确保催化裂化装置原料供应的前提下能够稳定生产低硫重质船用燃料油调合组分.

The strategy of adding tetralin as a H-donor in the thermal processing of heavy oil was investigated by exper-imental characterization and theoretical calculations. According to the experiments, the timing of adding 1 wt% of tetralin has a great influence on the visbreaking performance of heavy oil. Calculations based on density functional theory showed that benzyl radicals released from the thermal cracking of tetralin accelerate the dealkylation that determines the heavy oil upgrading. Meanwhile, H alpha provided by tetralin is able to selectively saturate aromatic C radicals which are essential for condensation. Compared with the conventional H-donor addition, i.e., pre-mixing of tetralin with heavy oil, a similar viscosity reduction rate of about 98% can be ob-tained during the visbreaking with delayed tetralin addition. Furthermore, the addition of tetralin before the significant occurrence of condensation further increases the conversion of vacuum residue fraction by 3.4% and reduces the asphaltene content of the product by 2.6 wt%.

采用微型高通量加氢实验装置对柴油加氢过程中的化学氢耗进行研究,将化学方程法计算得到的氢耗数据带入幂函数方程,建立了单一催化剂(CoMo或NiMo催化剂)沿反应器轴向加氢反应动力学模型.研究发现:将所建立的CoMo和NiMo的单一催化剂动力学模型进行组合可用于预测催化剂级配体系的氢耗数据;与单一NiMo催化剂装填方案相比,NiMo和CoMo混合级配由上至下的装填方案V(NiMo)/V(CoMo)=3时的氢耗更低,总氢耗降低了8.4％;且动力学拟合值与实验计算值的相对误差为4.5％.

In this paper, hydrogenation of CH to CH2 (HDCH reaction) was employed to simulate the hydrogen consumption during residue hydrotreating, because the pseudo components, CH and CH2, can be converted with the content of C and H. Through a pilot-scale experiment, a kinetic model for the HDCH reaction was constructed and it has high accuracy. By analyzing the running data of an industrial-residue hydrotreating unit, the activity change of the HDCH reaction was obtained using the active-region-migration deactivation model. The obtained HDCH activity model has high accuracy, where the frequencies of >10% relative errors are less than 1% for the CH and H contents. The hydrogen consumption model, the coupling of the HDCH kinetic model and the HDCH deactivation model, can be applied to calculate the hydrogen consumption. For case 2, where the hydrogen consumption model is adjusted every 100 days, the calculated data well match the real data compared to case 1, where the hydrogen consumption model is unadjusted over the whole runtime.

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.

The impacts of Fe , Co and Mo on the electronic structure of Ni2 P and the hydrodesulfurization (HDS) performance of 4 ,6-DMDBT were systematically studied by means of XRD ,TEM ,XPS and CO infrared adsorption .Characterization results show that the three doping metals can better adjust the electronic states of Ni2 P sites ,thereby affecting the adsorption energy of sulfur organic compounds on these sites .HDS performance assessment results indicate that there is a volcano-type relationship between HDS intrinsic activity and electronic structures of Ni2P sites , so that Co-Ni2 P/SiO2 with a moderate electron density has the best HDS activity due to moderate absorption energy .Furthermore ,the electron defects of Ni2 P can significantly facilitate the direct desulfurization (DDS) selectivity .Compared with Ni2P/SiO2 ,Ni2P in Mo-Ni2P/SiO2 has more electron defects and exhibits a higher DDS selectivity ,while that in Fe-Ni2 P/SiO2 and Co-Ni2 P/SiO2 has a lower DDS selectivity due to higher electron density .

中国石化石油化工科学研究院开发的加氢催化剂满足了全加氢炼油企业的需求,同时基于国家需求和行业环保法规要求,提出了加氢催化剂全生命周期绿色供应链理念并进行技术开发,包括载体材料和加氢催化剂绿色生产、器外真硫化、器外再生和废催化剂梯级利用等技术.载体材料和催化剂绿色生产及催化剂器外再生技术已经工业化多年,加氢催化剂器外真硫化技术于2018年进行了首次工业化应用,废渣油加氢催化剂再生、废馏分油加氢催化剂的梯级利用实验室研发取得较大进展.加氢催化剂全生命周期绿色供应链技术不仅能保证加氢催化剂工业应用过程中生产出绿色环保和高价值的产品,同时可保证催化剂生产和炼油厂装置开停工等过程都使用或未来能使用绿色环保技术,因此可全面助力资源的高效环保利用和促进整个炼油行业的绿色健康发展和可持续发展.

开发了以渣油为原料的化工型加氢-催化裂解双向组合技术:以渣油为原料,将催化裂解副产的富含多环芳烃的轻、重循环油掺入到渣油中一起加氢,然后再进行催化裂解,生产低碳烯烃和轻质芳烃等化工原料。加氢后,催化裂解轻、重循环油中的多环芳烃可以饱和为环烷环并芳环的分子结构,重新具有了可催化裂解性能,因此在渣油加氢和催化裂解的大循环中可大幅提高低碳烯烃和轻质芳烃的收率。以新鲜渣油进料为基准,双向组合模式中（低碳烯烃+轻质芳烃）收率为55.01%,远高于常规模式中（低碳烯烃+轻质芳烃）收率（42.57%）。

考察了加氢工艺条件对高硫渣油加氢脱硫反应效果的影响,结果表明:提高反应温度、降低空速有利于提高加氢脱硫反应活性;降低反应温度、降低氢分压及提高空速有利于提高加氢脱硫选择性.在达到相同脱硫率的情况下,提高反应温度可以采用更高的反应空速,从而降低渣油加氢的加工成本.渣油加氢-延迟焦化组合工艺的研究结果表明:随着加氢脱硫深度增加,加氢渣油中剩余的含硫化合物更倾向于生成石油焦;组合工艺可以大幅降低石油焦硫质量分数到3.0％以下,满足低硫焦的指标要求;与单独延迟焦化工艺相比,组合工艺可以生产更多更优质的高价值产品.

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.

在VB软件中运用单个TextBox控件拓展了 MSHFlexGrid控件的功能,主要实现了 MSHFlex-Grid控件中任意网格内容的可编辑功能、二维选区内多网格内容的同步传值和同步删除功能,同时给出了上下左右箭头键及回车键在MSHFlexGrid控件网格间光标移动的解决方案.其中,二维选区内多网格内容的同步赋值功能实现了将Excel、Txt和Word等文件的数据表数据,向MSHFlexGrid控件内指定二维多网格区域进行粘贴传值的操作.基于此,将MSHFlexGrid控件的拓展功能在具体化工软件中进行了实现.

The molecular structure of sulfur compounds in residual oils and their desulfurization reactivity during residue hydmprocessing (RHT) process were investigated by virtue of the self-established semiquantitative APPI FT-ICT MS combined with the kinetic analysis of the hydrodesulfurization of individual sulfur compounds. In order to increase the characterization accuracy and gain more structure details on the sulfur compounds, a prior SARA separation scheme of residual oils into clearly-defined fractions was performed. Results show that S1, 52, 53, and N1S1 class were the dominated species in the residual oil feedstock. During RHT process, the S1 class species were identified as the key refractory sulfur compounds, while 52 and 53 class species were identified as the easily-removed sulfur compounds. The molecular structure change of S1 class species during RHT process was marked by a drastic increase in the aromaticity and polycondensation, indicating that S1 class species with less-aromatic cores exhibited higher reactivity. Moreover, a novel DBE-based lumping kinetics approach containing 6 sulfur groups of S1 class compounds was developed to investigate the desulfurization reactivity of individual sulfur compounds. The results revealed that the reactivity of sulfur compounds depends on their structure, and different molecular structure brings distinctly different reactivity. The reactivity difference between the individual sulfur compounds in residual oils is considerably smaller than that in other petroleum fractions with lower boiling points, such as VGO, diesel. This research provides a deep insight into complex desulfurization chemistry during RHT process.

To achieve high-efficiency viscosity reduction in a mild hydrothermal environment, the visbreaking of heavy oil in a mixed solvent of subcritical water (sub-CW) and light aromatics was investigated. By solubilizing sub-CW in heavy oil, the dealkylation involved in visbreaking follows not only a free radical mechanism but also an ionic mechanism. The further introduction of light cycle oil rich in light aromatics but containing olefin groups has a complicated influence on visbreaking. Because of the presence of olefin groups, the viscosity reduction efficiency is initially reduced. In addition, the condensation to asphaltenes is promoted in the late visbreaking stage. However, these adverse effects are offset by the promotion of the solubilization of sub-CW in heavy oil by light aromatics. With enhanced dealkylation in both free radical and ionic mechanisms, a viscosity reduction rate of over 90% and reduced asphaltene formation can be obtained in the middle stage of visbreaking.

Molecular-level structures and distribution of refractory polycyclic aromatic sulfur heterocycles (PASHs) during residue hydrotreating process (RHT) are investigated. A prior atmospheric pressure photoionization (APPI) FT-ICR MS was used to obtain the distribution of refractory PASHs. Then the key refractory PASHs were further dissociated by collision-induced dissociation (CID) to identify the isomers and gain their fragment ions. During deep hydrodesulfurization (HDS), S1 class compounds detected in the RHT products was identified as the major refractory sulfur compounds. Moreover, an increase in the aromatic structure of S1 class species is present during RHT. The key refractory PASHs are these with DBE = 9-12, which also determine HDS depth during RHT process. From the CID experiments, as indicated by an increase of abundance of fragmentation of alkyl(C1-C4)-substituted DBT, alkyl(C2)-substituted DBT in particular, these key refractory PASHs have a structure of alkyl (C2)-substituted DBT, such as 4,6-DMDBT. In addition, the molecular chemical formula and molecular struc-ture for these key refractory PASHs were proposed, shedding a light on the development of industrial HDS catalysts and optimization of RHT process

通过研究不同工艺条件(反应温度、压力和体积空速)对高硫渣油加氢处理反应的影响,构建了高硫渣油加氢脱硫、加氢脱氮、加氢脱残炭、加氢脱金属反应的动力学模型,并与颗粒活性区迁移模型(失活模型)进行耦合,从而利用耦合模型对渣油加氢装置的升温曲线、非常规操作及产品性质进行了模拟预测.模拟结果表明:经耦合模型模拟所得各反应转化率的预测值与试验值吻合度高;在加氢催化剂的整个评价周期内,随着加氢催化剂金属沉积比例增加,各反应转化率均呈现初期快速下降、中期缓慢下降、末期快速下降的规律;模拟产品性质恒定条件下加氢脱硫、加氢脱氮和加氢脱残炭反应的升温曲线,可以得到装置推荐的升温曲线.

This article reports a new catalyst deactivation model for residue hydrotreating technology (RHT) with three adjustable parameters, named as "active-region-migration model". The active-region-migration model is proposed to describe the catalyst deactivation of RHT where the catalysts are deactivated due to metal loading. Along with the lumped reaction kinetics, the deactivation model can be applied to simulate the hydrogenation reaction performance in RHT. Industrial data from a commercial RHT unit show reasonably good agreements with the model calculations. Essentially, the active-region-migration model can separately simulate the catalytic-activity-change of each hydrogenation reaction during the whole run of RHT, with a single curve.

分别以中东高硫渣油及其与催化裂化柴油(简称催化柴油)的混合油为原料开展中型加氢试验,结果表明,催化柴油掺入渣油中混合加氢时,反应性能较好,加氢催化剂积炭量降低.催化柴油掺入渣油加氢的RICP-Ⅱ工艺在3家公司的工业应用结果表明:A公司渣油加氢装置第四周期催化剂沉积金属量和平均积炭量低于第二周期;B公司渣油加氢装置掺入催化柴油后反应器总压降明显下降,径向温差明显降低,总温升有所上升,对加氢脱硫、加氢脱氮及残炭加氢转化反应均有促进作用,但对脱金属反应的促进效果不明显;C公司渣油加氢装置高比例掺入催化柴油,在加工总量中催化柴油质量占比26.33％、催化柴油占反应总进料质量比例最高值达45％以上的情况下,1261 d的运行周期内反应系统总压降低于2.0 MPa、温升低于70℃、最大径向温差低于9℃.