The influences of reaction temperature, duration, pressure, and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated. The molecular composition of the heteroatom compounds in the residue feedstock and its upgrading products were characterized using high-resolution Orbitrap mass spectrometry coupled with multiple ionization methods. The simultaneous promotion of cracking and hydrogenation reactions was observed with increasing of the reaction temperature and time. Specifically, there was a significant increase in the cracking degree of alkyl side chain, while the removal of low-condensation sulfur compounds such as sulfides and benzothiophenes was enhanced. In particular, the cracking reactions were more significantly facilitated by high temperatures, while an appropriately extended reaction time can result in the complete elimination of the aforementioned sulfur compounds with a lower degree of condensation. Under conditions of low hydrogen pressure and catalyst concentration, the products still exhibit a high relative abundance of easily convertible compounds such as sulfoxides, indicating a significant deficiency in the effectiveness of hydrogenation. The hydrogen pressure exhibits an optimal value, beyond which further increments have no effect on the composition and performance of the liquid product but can increase the yield of the liquid product. At significantly high catalyst concentration, the effect of desulfurization and deoxidation slightly diminishes, while the aromatic saturation of highly condensed compounds was notably enhanced. This hydrogenation saturation effect cannot be attained through manipulation of other operational parameters, thereby potentially benefiting subsequent product processing and utilization. This present study demonstrates a profound comprehension of the molecular-level residue slurry phase hydrocracking process, offering not only specific guide for process design and optimization but also valuable fundamental data for constructing reaction models at the molecular level.

Heavy oil is an important resource in current petroleum exploitation, and the chemical composition information of heavy oil is crucial for revealing its viscosity-inducing mechanism and solving practical exploitation issues. In this study, the techniques of high-temperature gas chromatography and high-resolution mass spectrometry equipped with an electrospray ionization source were applied to reveal the chemical composition of typical heavy oils from western, central, and eastern China. The results indicate that these heavy oils display significant variations in their bulk properties, with initial boiling points all above 200 ℃. Utilizing pre-treatment and ESI high-resolution mass spectrometry, an analysis of the molecular composition of saturated hydrocarbons, aromatic hydrocarbons, acidic oxygen compounds, sulfur compounds, basic nitrogen compounds, and neutral nitrogen compounds within the heavy oil was conducted. Ultimately, a semi-quantitative analysis of the molecular composition of the heavy oil was achieved by integrating the elemental content. The semi-quantitative analysis results of Shengli-J8 heavy oil and a conventional Shengli crude oil show that Shengli-J8 heavy oil lacks alkanes and low molecular weight aromatic hydrocarbons, which contributes to its high viscosity. Additionally, characteristic molecular sets for different heavy oils were identified based on the semi-quantitative analysis of molecular composition. The semi-quantitative analysis of molecular composition in heavy oils may provide valuable reference data for establishing theoretical models on the viscosity-inducing mechanism in heavy oils and designing viscosity-reducing agents for heavy oil exploitation.

Refinery sour water primarily originates from the tops of towers in various units and coker condensate, and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand (COD) and organic sulfur contents. Even after the recovery of H₂S from the sour water by the stripping process, the effluent still contains a high concentration of dissolved organic sulfur (DOS), which can have a huge bad influence. While chemical composition of dissolved organic matter (DOM) in refinery wastewater has been extensively studied, the investigation of recalcitrant DOS from sour waters remains unclear. In the present study, chemical composition of sour water DOMs (especially DOS) was investigated using fluorescence spectroscopy (excitation-emission matrix, EEM) and mass spectrometry, including gas chromatography-mass spectrometry (GC-MS) and high-resolution Orbitrap MS. The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process, while compounds with high hydrophilicity and humification degree were found to be more recalcitrant. The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds. However, the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms, particularly in the form of highly unsaturated and aromatic compounds. The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates, disulfide bonds, thioethers. Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

Steam flooding is a widely used technique to enhance oil recovery of heavy oil. Thermal viscosity reduction and distillation effect are considered as two main displacement mechanisms in steam flooding process. However, the molecular composition understanding and contribution for oil production are still unclear. In this study, the composition analysis of the heavy oil was investigated in the core scale steam flooding process with the temperature from 120 to 280 ℃. The crude oil, produced oils and residual oils were characterized comprehensively by gas chromatography and high-resolution mass spectrometry. It is found that steam flooding preferentially extracts aromatics and remains more resins in the residual oil. Viscosity reduction is the dominant mechanism when steam is injected at a low temperature. Large molecular heteroatoms with high carbon number and high double bond equivalent (DBE) are eluted into the produced oil, while compounds with low carbon number and low DBE are remained in the residual oil. As the steam temperature rises, the increased distillation effect results in the extraction of light hydrocarbons from the residual oil to the produced oil. More small heteroatoms with low carbon number and low DBE enter into the produced oil, especially in the none water cut stage. The compositional difference of produced oils is characterized in DBE versus carbon number distribution of the N and O containing compound classes. This work uses a variety of composition analysis methods to clarify the steam flooding mechanism and provides a novel understanding of steam flooding mechanisms with various temperatures and production stages from the molecular perspective.

Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions; the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction; the total acid number of the heavy distillates is higher than that of the residue fraction; the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.