Concentrations of vanadium and nickel and their ratio in heavy oil asphaltenes

Yakubov, M. R.; Milordov, D. V.; Yakubova, S. G.; Borisov, D. N.; Ivanov, V. T.; Sinyashin, Kirill

doi:10.1134/s0965544116010072

Cited by 35 publications

(22 citation statements)

References 3 publications

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“…Our initial efforts were directed toward synthesizing AO using Hummers' method 18 , which is commonly used to oxidize graphite to GO. Asphaltene was treated with a 1:4.3 w/w mixture of sulfuric acid and potassium permanganate at 35°C for 3 h, and then washed with an aqueous solution of HCl (1.0 M) followed by deionized water to extract heavy metal impurities (e.g., vanadium and nickel) 19 . The resulting product featured a relatively high oxygen content (~13.1 wt%; c.f., a~1.4 wt% oxygen content that was measured for the starting material), as determined using elemental analysis (see Supplementary Table 1), as well as strong IR absorption bands that were assigned to hydroxyl (ν O-H = 3400 cm −1 ), carbonyl (ν C=O = 1700 cm −1 ), and epoxide (ν C-O = 1220 and 1160 cm −1 ) stretching frequencies (see Fig.…”

Section: Resultsmentioning

confidence: 99%

Asphaltene oxide promotes a broad range of synthetic transformations

Jung

Bielawski

2019

Commun Chem

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Carbocatalysts, which are catalytically-active materials derived from carbon-rich sources, are attractive alternatives to metal-based analogs. Graphene oxide is a prototypical example and has been successfully employed in a broad range of synthetic transformations. However, its use is accompanied by a number of practical and fundamental drawbacks. For example, graphene oxide undergoes explosive decomposition when subjected to elevated temperatures or microwaves. We found that asphaltene oxide, an oxidized collection of polycyclic aromatic hydrocarbons that are often discarded from petroleum refining processes, effectively overcomes the drawbacks of using graphene oxide in synthetic chemistry and constitutes a new class of carbocatalysts. Here we show that asphaltene oxide may be used to promote a broad range of transformations, including Claisen-Schmidt condensations, CC cross-couplings, and Fischer indole syntheses, as well as chemical reactions which benefit from the use of microwave reactors.

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Section: Resultsmentioning

confidence: 99%

Asphaltene oxide promotes a broad range of synthetic transformations

Jung

Bielawski

2019

Commun Chem

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“…To obtain a deeper understanding of these variations, Ni/V ratios were extracted from the published literature for similar oils from different regions, plotted, and the scatter of the data studied. Figure 5 represents a plot of Ni/V ratios for Abu Dhabi crude oil, Russian crude and Venezuelan crude [3,5,16]. it is clear from the plot that distinct clusters exist within a group of oils (encircled).…”

Section: Variation In Ni/v Ratiosmentioning

confidence: 99%

“…The thrust of this work concerns the development of a rapid laser technique [1,2] for deriving Ni/V ratios in solid asphaltene matrices. The traditional method for obtaining these ratios is solvent digestion [3], which is usually time-consuming and tedious. There is a need therefore, to obviate the lengthy procedure and save chemical resources.…”

Section: Introductionmentioning

confidence: 99%

“…There is a need therefore, to obviate the lengthy procedure and save chemical resources. In the petroleum industry, the nickel/vanadium ratio is considered to be a popular 'damage control' parameter, especially in chemical refining processes [3]. These ratios are also employed by petroleum engineers to garner definite types of pre-historic geoscience information [4].…”

Section: Introductionmentioning

confidence: 99%

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Deep-UV Laser Ablation Technology [213 nm] Coupled with Plasma Quadrupole Mass Spectrometry for Rapid Determination of Nickel/ Vanadium Ratios in Asphaltenes

Ae¹,

AA²

2016

Mass Spectrom Purif Tech

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Knowledge of nickel/vanadium (Ni/V) ratios in petroleum fuel is essential to source geochemical information and to limit catalytic poisoning and corrosive effects in chemical refining processes. However, these ratios have been found to vary widely and are affected by various factors, including the sulphur content of the petroleum feedstock. They are normally obtained by digesting and treating the feedstock in suitable acid or organic media followed by numerical analysis. Our research investigated a novel sample introduction technique for obtaining Ni/V ratios by ablating petrified asphaltene samples (following liquid nitrogen pre-treatment) with a 213 nm laser beam coupled to a hyphenated plasma mass spectroscopic system. Laser ablation is ideal for delving beneath the surface of a solid matrix to measure the composition of the substrate. Iterative scanning of the sample surface and subsequent depth-profiling was achieved at predetermined surface points to depths of 50 μm at selected sub-surface intervals. Characteristic intensities originating from the metals of interest were measured. Laser results were compared with the 'digested' results obtained directly by ICP-MS. In the case of the digested crude oil samples, these ratios varied between 0.6 and 0.8. This was higher than corresponding literature values, which occurred within a range of 0.3-0.6. The laser ablation results for typical asphaltene samples showed that Ni/V ratios varied in the interval 0.2-0.8, which were considered to be elevated and in keeping with the elevated crude oil ratios. The digested asphaltenes also reflected higher ratios, suggesting the influence of sample inhomogeneity and nickel impurities. Factors affecting variations in this ratio are presented, and the advantages of a more stable ratio are discussed. The study is of definite interest to petroleum engineers, and has considerable scope for extended research.

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“…Crude oil is a complex mixture containing heteroatoms such as sulfur, and heavy metals like nickel and vanadium [2]. Vanadium and nickel are known to be present in petroleum up to few hundred parts per million [3,4]. To improve demetallation and hydrodesulfurization processes, a better understanding of metal speciation is necessary, which has led to a growing interest in hyphenated techniques, which can combine the high separation power of ultra-high performance liquid chromatography (UHPLC) to a specific detection such as inductively coupled plasma mass spectrometer (ICP-MS/MS).…”

Section: Introductionmentioning

confidence: 99%

Comprehensive two-dimensional liquid chromatography with inductively coupled plasma mass spectrometry detection for the characterization of sulfur, vanadium and nickel compounds in petroleum products

Bernardin

Masle

Bessueille-Barbier

et al. 2020

Journal of Chromatography A

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The petroleum industry is increasingly concerned with the conversion of vacuum residues as a consequence of decreased conventional crude oil availability. The compositional analysis of heavy oil products has become a key step in conversion processes, but the complexity of these oil matrices tends to increase with their boiling point. In this study, comprehensive two-dimensional liquid chromatography (LCxLC) coupled to inductively coupled mass spectrometry (ICP-MS/MS) is considered with a view to meet new requirements and to bring additional information regarding the species present in these matrices. In search for a high degree of orthogonality, two separation techniques involving two different retention mechanisms were evaluated: Size Exclusion Chromatography (SEC) and Reverse Phase Liquid Chromatography (RPLC). In SEC, the analytes are separated according to their molecular weight while according to their hydrophobicity in RPLC. The separation power of both individual separation techniques was first evaluated. Off-line and on-line LCxLC were compared on the basis of an optimization approach. It is shown that off-line SECxRPLC can provide, for the same analysis time of 150 min, a higher peak capacity (2600 vs 1700) while a similar dilution factor (close to 30) but also requires far fewer fractions to be analyzed (12 vs 2 400). Asphaltenes which constitute the heaviest fraction of crude oils (obtained from petroleum industry) were analyzed by the developed off-line SECxRPLC method. The resulting 2D-contour plots show that co-elutions could be removed leading, for the first time, to new information on high molecular weight species containing sulfur and vanadium.

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Concentrations of vanadium and nickel and their ratio in heavy oil asphaltenes

Cited by 35 publications

References 3 publications

Asphaltene oxide promotes a broad range of synthetic transformations

Asphaltene oxide promotes a broad range of synthetic transformations

Deep-UV Laser Ablation Technology [213 nm] Coupled with Plasma Quadrupole Mass Spectrometry for Rapid Determination of Nickel/ Vanadium Ratios in Asphaltenes

Comprehensive two-dimensional liquid chromatography with inductively coupled plasma mass spectrometry detection for the characterization of sulfur, vanadium and nickel compounds in petroleum products

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